You searched for subject:(C C Activation).
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University of Minnesota
1.
Rondla, Naveen Reddy.
Development of new reaction methodologies using palladium catalysts.
Degree: PhD, Chemistry, 2014, University of Minnesota
URL: http://hdl.handle.net/11299/165789 
► Chapter 1: This chapter provides a brief review of the chemistry of metal catalyzed C-C sigma-bond activation reactions. Literature examples for a variety of methods…
(more)
▼ Chapter 1: This chapter provides a brief review of the chemistry of metal catalyzed C-C sigma-bond activation reactions. Literature examples for a variety of methods to activate C-C sigma-bonds and their limitations are discussed in detail. Introduction to C-CN sigma-bond reaction and its advantages over the typical C-C sigma-bond activation reactions are discussed with literature examples. Motivation for the current work is also presented.Chapter 2: Presented herein development of new reaction methodology, intramolecular cyanoesterification of alkynes to synthesize highly functionalized butenolides. The reaction proceeds with commonly used palladium catalyst (Pd(PPh3)4) under microwave conditions in five minutes. The reaction tolerates wide variety of substrates and corresponding results are presented. Plausible mechanistic hypothesis is also discussed. Chapter 3: Presented herein new methodology for intramolecular cyanoacylation of alkenes to synthesize highly functionalized indanones . The major challenge of decarbonylation has been overcome using iminonitriles. The reaction proceeds in the presence of commonly used palladium catalyst (Pd(PPh3)4) and very common Lewis acid ZnCl2. The reaction tolerates wide variety of substrates and corresponding results are presented. Results of mechanistic study of the reaction and plausible mechanism are also presented.Chapter 4: Presented herein our attempt towards development of intramolecular azidocyanation of alkenes using carbamoyl azides. Interestingly instead of azidoacylation product, 2-quinazolinone was isolated by the loss of CH2 and N2. Future work on optimization and applications of this interesting reaction are discussed.
Subjects/Keywords: Catalysis; C-C Activation; Palladium
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APA (6th Edition):
Rondla, N. R. (2014). Development of new reaction methodologies using palladium catalysts. (Doctoral Dissertation). University of Minnesota. Retrieved from http://hdl.handle.net/11299/165789
Chicago Manual of Style (16th Edition):
Rondla, Naveen Reddy. “Development of new reaction methodologies using palladium catalysts.” 2014. Doctoral Dissertation, University of Minnesota. Accessed December 08, 2019.
http://hdl.handle.net/11299/165789.
MLA Handbook (7th Edition):
Rondla, Naveen Reddy. “Development of new reaction methodologies using palladium catalysts.” 2014. Web. 08 Dec 2019.
Vancouver:
Rondla NR. Development of new reaction methodologies using palladium catalysts. [Internet] [Doctoral dissertation]. University of Minnesota; 2014. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/11299/165789.
Council of Science Editors:
Rondla NR. Development of new reaction methodologies using palladium catalysts. [Doctoral Dissertation]. University of Minnesota; 2014. Available from: http://hdl.handle.net/11299/165789
University of California – Berkeley
2.
Bowring, Miriam Anna.
Hydrocarbon Bond Activation with Platinum(II) Complexes.
Degree: Chemistry, 2013, University of California – Berkeley
URL: http://www.escholarship.org/uc/item/93242966
► Chapter 1. The hydroarylation of unactivated olefins effected by Pt(II) precatalysts is found to proceed through the in situ production of protic acid followed by…
(more)
▼ Chapter 1. The hydroarylation of unactivated olefins effected by Pt(II) precatalysts is found to proceed through the in situ production of protic acid followed by a Friedel-Crafts mechanism. The reaction is investigated using the hindered base 2,6-di-tert-butyl-4-methylpyridine and a variety of substrates. Chapter 2. The catalytic cleavage of two C-C single bonds is achieved by treatment of the hydrocarbon substrate spiro[bicyclo[2.2.1]hept-2-ene-7,1'-cyclopropane] with Pt(II) catalysts such as (Me2bpy)PtPh(NTf2) (Me2bpy = 4,4'-dimethyl-2,2'-bipyridine, NTf2- = N(SO2CF3)2-). The surprising rearrangement product 1,2,4,7,7-pentahydroindene is generated in good yield. The mechanism of C-C bond activation is investigated using NMR spectroscopy, electrospray ionization mass spectrometry, and deuterium labeling, along with DFT calculations. These studies support an unusual catalytic mechanism in which an initial masked C-H bond activation initiates successive C-C bond cleavage events.Chapter 3. A dicationic Pt complex [(tBu2bpy)Pt](NTf2)2·½ C6H6 (tBu2bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) is isolated and characterized. The new complex is supported by a simple bidentate bipyridine ligand and weakly coordinating, easily displaced triflimidate counterions. The dication is competent for allylic C-H activation in aprotic, non-polar media.
Subjects/Keywords: Chemistry; catalysis; C-C activation; C-H activation; mechanism; organometallics; platinum
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APA (6th Edition):
Bowring, M. A. (2013). Hydrocarbon Bond Activation with Platinum(II) Complexes. (Thesis). University of California – Berkeley. Retrieved from http://www.escholarship.org/uc/item/93242966
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Bowring, Miriam Anna. “Hydrocarbon Bond Activation with Platinum(II) Complexes.” 2013. Thesis, University of California – Berkeley. Accessed December 08, 2019.
http://www.escholarship.org/uc/item/93242966.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Bowring, Miriam Anna. “Hydrocarbon Bond Activation with Platinum(II) Complexes.” 2013. Web. 08 Dec 2019.
Vancouver:
Bowring MA. Hydrocarbon Bond Activation with Platinum(II) Complexes. [Internet] [Thesis]. University of California – Berkeley; 2013. [cited 2019 Dec 08].
Available from: http://www.escholarship.org/uc/item/93242966.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Bowring MA. Hydrocarbon Bond Activation with Platinum(II) Complexes. [Thesis]. University of California – Berkeley; 2013. Available from: http://www.escholarship.org/uc/item/93242966
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Rochester
3.
Wilklow-Marnell, Miles.
Manipulation of carbon-element bonds by Pincer ligated
iridium complexes.
Degree: PhD, 2017, University of Rochester
URL: http://hdl.handle.net/1802/33156
► Since the seminal contributions of Moulton and Shaw in the 1970’s, who synthesized the first “pincer” complexes, including tBuPCPIrHCl (tBuPCP = κ3-2,6-C6H3(CH2P(tBu)2)2), the chemistry of…
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▼ Since the seminal contributions of Moulton and Shaw
in the 1970’s, who synthesized the first “pincer” complexes,
including tBuPCPIrHCl (tBuPCP = κ3-2,6-C6H3(CH2P(tBu)2)2), the
chemistry of transition metal complexes ligated by tri-dentate,
planar, pincer-type ligands has experienced vast development.
Pincer-complexes of 1st, 2nd, and 3rd row transition metals are now
known, and have been employed in a number of useful processes such
as alkane, alcohol, and N-heterocycle dehydrogenation, Heck
coupling, and C-H borylation reactions. In the Jones lab at the
University of Rochester, we have found that the less bulky
iso-propyl substituted analog (iPrPCP) of Moulton and Shaw’s
original ligand facilitates greatly enhanced reactivity when bound
to iridium in comparison to its tert-butyl counterpart. For
example, the C-C cleavage of biphenylene by iPrPCPIr occurs in less
than 30 minutes at room temperature, while the same reaction
requires heating at 125 °C for 24 hours with tBuPCPIr. In some
cases, novel reactions not possible with tBuPCPIr have been
discovered. While iPrPCPIr was found to catalyze the
dehydrogenative coupling of un-functionalized vinyl arenes to form
1,4-butadienes at relatively low catalyst loadings (1-5 mole%),
tBuPCPIr did not produce any observable coupling products. Also,
iPrPCPIr(PhC≡CPh) was found to undergo isomerization to a unique
iridaindene product when heated at 100 °C, whereas only
decomposition occurred with tBuPCPIr(PhC≡CPh). These
transformations, and others, mediated by iPrPCPIr are
discussed.
Subjects/Keywords: C-C activation; C-H activation; Cyclometalation; Dehydrogenative coupling; Iridaindene; Quinones
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APA ·
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APA (6th Edition):
Wilklow-Marnell, M. (2017). Manipulation of carbon-element bonds by Pincer ligated
iridium complexes. (Doctoral Dissertation). University of Rochester. Retrieved from http://hdl.handle.net/1802/33156
Chicago Manual of Style (16th Edition):
Wilklow-Marnell, Miles. “Manipulation of carbon-element bonds by Pincer ligated
iridium complexes.” 2017. Doctoral Dissertation, University of Rochester. Accessed December 08, 2019.
http://hdl.handle.net/1802/33156.
MLA Handbook (7th Edition):
Wilklow-Marnell, Miles. “Manipulation of carbon-element bonds by Pincer ligated
iridium complexes.” 2017. Web. 08 Dec 2019.
Vancouver:
Wilklow-Marnell M. Manipulation of carbon-element bonds by Pincer ligated
iridium complexes. [Internet] [Doctoral dissertation]. University of Rochester; 2017. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1802/33156.
Council of Science Editors:
Wilklow-Marnell M. Manipulation of carbon-element bonds by Pincer ligated
iridium complexes. [Doctoral Dissertation]. University of Rochester; 2017. Available from: http://hdl.handle.net/1802/33156
University of Illinois – Urbana-Champaign
4.
Liu, Wei.
Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis.
Degree: PhD, Chemistry, 2018, University of Illinois – Urbana-Champaign
URL: http://hdl.handle.net/2142/102431
► Asymmetric C–H functionalization could deliver a highly efficient transformation by installing both oxidized functionality and absolute stereochemistry simultaneously. In this context, palladium(II)-catalyzed asymmetric allylic C–H…
(more)
▼ Asymmetric C–H functionalization could deliver a highly efficient transformation by installing both oxidized functionality and absolute stereochemistry simultaneously. In this context, palladium(II)-catalyzed asymmetric allylic C–H functionalization of terminal olefins through the intermediacy of π-allyl/Pd(II) complex represents a viable platform. Traditionally, the asymmetric functionalization of π-allyl/Pd(II) intermediate generally proceeded with phosphine-based ligands, under redox-neutral and basic conditions. Current efforts to develop the oxidative allylic C–H functionalization reaction have focused on the adaptation of phosphine-based ligands, which are prone to oxidation. As such, these systems suffer from limited substrate scope (activated olefins, e.g. allylarenes) and modest enantioselectivity. Alternatively, the oxidatively stable bis-sulfoxide ligand has shown to promote general reactivity with broad scope. However, its underlying mechanism, known as “serial ligand catalysis”, is challenging for asymmetric catalysis, due to the highly dynamic and fluxional binding environment of palladium. This work describes the development of oxidatively stable, chiral sulfoxide-oxazoline ligands for palladium(II)-catalyzed asymmetric allylic C–H oxidations and alkylations. The design principle is to combine the sulfoxide moiety, known to promote C–H cleavage, with a strongly coordinately oxazoline moiety that can anchor the ligand to the metal and thereby provide a stable chiral environment. Additionally, the σ-donation from oxazoline could promote the formation of a cationic π-allyl/Pd(II) intermediate, which becomes more reactive towards functionalization.
The first chapter of this dissertation describes the development of a general intermolecular allylic C–H alkylation with tertiary nucleophiles under palladium(II)/bis-sulfoxide catalysis. This work laid the foundation for asymmetric processes with the resultant quaternary stereogenic centers that would not be prone to racemization. This reaction incorporates a broad scope of terminal olefins (e.g. aromatic, aliphatic) and tertiary nucleophiles (e.g. nitroketones, β-ketoesters) with good yields and excellent selectivities (>20:1 linear:branched, >20:1 E:Z). The use of tertiary nucleophiles allows for strategic incorporation of latent functionality into the alkylation partner, which can be exploited for further elaboration to generate molecular complexity. This concept is demonstrated in a tandem allylic C–H alkylation/Diels-Alder reaction sequence: a reactive diene is generated upon the alkylation of a terminal olefin and trapped by a dienophile contained within the tertiary nucleophile to afford a complex tricyclic core structure.
The second chapter describes the development of chiral sulfoxide-oxazoline (SOX) ligands for Pd(II)-catalyzed enantioselective allylic C–H oxidation. Chiral isochromans are formed by the intramolecular cyclization between alcohol and terminal olefin, leading to good yields and high enantioselectivities (>90% ee). Pd(II)/trans-SOX…
Advisors/Committee Members: White, Maria Christina (advisor), White, Maria Christina (Committee Chair), Denmark, Scott E (committee member), Hergenrother, Paul J (committee member), Fout, Alison R (committee member).
Subjects/Keywords: C–H Activation; Asymmetric Catalysis
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APA ·
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APA (6th Edition):
Liu, W. (2018). Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis. (Doctoral Dissertation). University of Illinois – Urbana-Champaign. Retrieved from http://hdl.handle.net/2142/102431
Chicago Manual of Style (16th Edition):
Liu, Wei. “Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis.” 2018. Doctoral Dissertation, University of Illinois – Urbana-Champaign. Accessed December 08, 2019.
http://hdl.handle.net/2142/102431.
MLA Handbook (7th Edition):
Liu, Wei. “Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis.” 2018. Web. 08 Dec 2019.
Vancouver:
Liu W. Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis. [Internet] [Doctoral dissertation]. University of Illinois – Urbana-Champaign; 2018. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/2142/102431.
Council of Science Editors:
Liu W. Asymmetric allylic C–H functionalization via palladium(II)/sulfoxide-oxazoline catalysis. [Doctoral Dissertation]. University of Illinois – Urbana-Champaign; 2018. Available from: http://hdl.handle.net/2142/102431
University of Illinois – Urbana-Champaign
5.
Sookezian, Anasheh.
Manganese-catalyzed intermolecular benzylic C–H amination.
Degree: MS, Chemistry, 2017, University of Illinois – Urbana-Champaign
URL: http://hdl.handle.net/2142/98303
► Reactions that directly install nitrogen into C—H bonds of complex molecules are significant due to their ability to immediately change the chemical and biological properties…
(more)
▼ Reactions that directly install nitrogen into C—H bonds of complex molecules are significant due to their ability to immediately change the chemical and biological properties of a given molecule. While selective intramolecular C—H amination reactions are known, intermolecular C—H amination reactions with high reactivity and selectivity are scarce. Achieving high levels of reactivity while maintaining excellent site-selectivity and functional group tolerance remains an important challenge for intermolecular C—H amination. We report a novel manganese perchlorophthalocyanine catalyst [Mn(ClPc)] for a highly site-selective intermolecular benzylic C—H amination of bioactive molecules and natural products. [Mn(ClPc)] is selective for benzylic C—H bonds over other C—H bond types and selects among multiple benzylic C—H bonds based on their electronic and steric properties.
Advisors/Committee Members: White, M. Christina (advisor).
Subjects/Keywords: Amination; Manganese; C–H activation
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APA (6th Edition):
Sookezian, A. (2017). Manganese-catalyzed intermolecular benzylic C–H amination. (Thesis). University of Illinois – Urbana-Champaign. Retrieved from http://hdl.handle.net/2142/98303
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Sookezian, Anasheh. “Manganese-catalyzed intermolecular benzylic C–H amination.” 2017. Thesis, University of Illinois – Urbana-Champaign. Accessed December 08, 2019.
http://hdl.handle.net/2142/98303.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Sookezian, Anasheh. “Manganese-catalyzed intermolecular benzylic C–H amination.” 2017. Web. 08 Dec 2019.
Vancouver:
Sookezian A. Manganese-catalyzed intermolecular benzylic C–H amination. [Internet] [Thesis]. University of Illinois – Urbana-Champaign; 2017. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/2142/98303.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Sookezian A. Manganese-catalyzed intermolecular benzylic C–H amination. [Thesis]. University of Illinois – Urbana-Champaign; 2017. Available from: http://hdl.handle.net/2142/98303
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
NSYSU
6.
Chiang, Meng-fan.
Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation.
Degree: Master, Chemistry, 2015, NSYSU
URL: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0604115-140952
► A direct ortho-aroylation of N-arylpyridin-2-amines with aldehydes to afford mono- and di-aroylated N-arylpyridin-2-amines in modest to good yields is presented. In the reaction, palladium(II) acetate,…
(more)
▼ A direct ortho-aroylation of N-arylpyridin-2-amines with aldehydes to afford mono- and di-aroylated N-arylpyridin-2-amines in modest to good yields is presented. In the reaction, palladium(II) acetate, tert-butyl hydroperoxide (TBHP), and 1,4-dioxane were used as the catalyst, oxidant, and solvent, respectively. The synthetic methodology serves good functional group compatibility. A possible catalytic mechanism is also presented.
Advisors/Committee Members: Jen-Chieh Hsieh (chair), Ming-Jung Wu (committee member), Po-Chiao Lin (chair).
Subjects/Keywords: palladium; C-C coupling; C-H activation; catalyzed reaction; ortho-aroylation
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APA (6th Edition):
Chiang, M. (2015). Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation. (Thesis). NSYSU. Retrieved from http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0604115-140952
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Chiang, Meng-fan. “Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation.” 2015. Thesis, NSYSU. Accessed December 08, 2019.
http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0604115-140952.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Chiang, Meng-fan. “Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation.” 2015. Web. 08 Dec 2019.
Vancouver:
Chiang M. Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation. [Internet] [Thesis]. NSYSU; 2015. [cited 2019 Dec 08].
Available from: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0604115-140952.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Chiang M. Palladium-Catalyzed Direct Ortho-Aroylation of N-Arylpyridin-2-amines with Aldehydes via C-H Activation. [Thesis]. NSYSU; 2015. Available from: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0604115-140952
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
NSYSU
7.
Chen, Jiun-hong.
Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one.
Degree: Master, Chemistry, 2016, NSYSU
URL: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0618116-111826
► A direct ortho-Arylation of 1-methyl-N-phenyl-1H-indole-3-carboxamide via Carbon-Hydride Bond Activation. In the reaction, Palladium(II) trifluoroacetate, Copper(II) acetate, Potassium phosphate, Pivalic acid, and DMF:1,4-Dioxane=1/9 were used as…
(more)
▼ A direct ortho-Arylation of 1-methyl-N-phenyl-1H-indole-3-carboxamide via Carbon-Hydride Bond
Activation. In the reaction, Palladium(II) trifluoroacetate, Copper(II) acetate, Potassium phosphate, Pivalic acid, and DMF:1,4-Dioxane=1/9 were used as the catalyst, oxidant, base, and solvent. The synthetic methodology serves good functional group compatibility.
Advisors/Committee Members: Jiann-Jyh Huang (chair), Ming-Jung Wu (committee member), Jen-Chieh Hsieh (chair).
Subjects/Keywords: palladium; ortho-aroylation; C-C coupling; catalyzed reaction; C-H activation
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APA ·
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APA (6th Edition):
Chen, J. (2016). Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one. (Thesis). NSYSU. Retrieved from http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0618116-111826
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Chen, Jiun-hong. “Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one.” 2016. Thesis, NSYSU. Accessed December 08, 2019.
http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0618116-111826.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Chen, Jiun-hong. “Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one.” 2016. Web. 08 Dec 2019.
Vancouver:
Chen J. Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one. [Internet] [Thesis]. NSYSU; 2016. [cited 2019 Dec 08].
Available from: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0618116-111826.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Chen J. Palladium-Catalyzed Direct Carbon-Hydrogen Activation Reaction to 1-methyl-N-phenyl-1H-indole-3-carboxamide to 11-methyl-5H-indolo[3,2-c]quinolin-6(11H)-one. [Thesis]. NSYSU; 2016. Available from: http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0618116-111826
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Rochester
8.
Evans, Meagan Elizabeth (1981 - ).
I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile.
Degree: PhD, 2011, University of Rochester
URL: http://hdl.handle.net/1802/14773
► Several transition-metal systems have been used to establish correlations between metal-carbon and carbon-hydrogen bonds. In the following studies, the [Tp’RhL] fragment where Tp’ = tris(3,5-dimethylpyrazolyl)borate…
(more)
▼ Several transition-metal systems have been used to
establish correlations between metal-carbon and carbon-hydrogen
bonds. In the following studies, the [Tp’RhL] fragment where Tp’ =
tris(3,5-dimethylpyrazolyl)borate and L = neopentyl isocyanide, is
used to investigate C–H bond activation of molecules with strong
C–H bonds. The first study (Chapter 2) examines C–H bond activation
of fluorinated aromatic hydrocarbons. Photolysis of the precursor,
Tp’RhL(carbodiimide) in neat fluoroarene resulted in C–H activation
products of the type, Tp’RhL(arylF)H. Both the kinetic and
thermodynamic selectivities of rhodium for different C–H bonds on
the fluorinated aromatic were examined. A strong thermodynamic
preference was observed for C–H activation ortho to two fluorine
atoms as opposed to one. Competition experiments along with ΔGre≠
values allow for the determination of relative Rh–Caryl bond
strengths and illustrate the large ortho fluorine effect on the
strength of the Rh–Caryl bond. This study was the first to quantize
experimentally the effect of an ortho fluorine on the strength of
the metal–carbon bond.
In a similar study, the [Tp’RhL] fragment
was used to investigate C–H bond activation of a series of linear
alkylnitriles and chloroalkanes (Chapter 3). The selectivity of
[Tp’RhL] for C–H bonds of alkylnitriles and chloroalkanes has been
previously studied, but the Rh–C bond strengths could not be
determined. New experiments and insight allowed for the
determination of relative Rh–C bond strengths of these C–H
activation complexes. It is found that the CN and Cl substituents
dramatically strengthen the M–C bond more than anticipated if in
the [alpha]-position, with the effect on bond strength diminishing
substantially as these groups move further from the metal (i.e,
[beta], [gamma], [delta]). Examination of M–C vs. C–H bond
strengths allows for the quantization of resonance stabilization on
metal–carbon bonds.
The work in Chapter 4 represents the first
example of C–C cleavage by oxidative addition of the C–CN bond to a
Rh(I) center. Here, the selectivity of the [Cp*Rh(PMe3)] fragment
for both C–H and C–C bonds of acetonitrile is examined. Low
temperature photolysis of Cp*Rh(PMe3)H2 in neat acetonitrile gives
only the C–H activation product. Upon heating, this product is
completely converted to the C–CN activation product. Density
functional theory (DFT) was used to identify the transition states
for C–H and C–C activation along with the ground state energies for
all possible products. DFT calculations are in excellent agreement
with the experimental observations and predict C–H activation to be
kinetically favored by ~2 kcal/mol, and show a large thermodynamic
preference for C–C activation (ΔG° ≈13 kcal/mol).
Recent results
in our group have shown the importance of the ancillary ligand on
the ability of rhodium to cleave a C–CN bond. A rhodium metal
fragment with a π-acceptor ligand in place of a [sigma]-donating
ligand shows exclusive selectivity for C–H activation, and does not
show the same ability to cleave a…
Subjects/Keywords: Bond energies; Bond strength; C-H bond activation; Orthofluorine effect; C-C activation
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APA (6th Edition):
Evans, M. E. (. -. ). (2011). I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile. (Doctoral Dissertation). University of Rochester. Retrieved from http://hdl.handle.net/1802/14773
Chicago Manual of Style (16th Edition):
Evans, Meagan Elizabeth (1981 - ). “I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile.” 2011. Doctoral Dissertation, University of Rochester. Accessed December 08, 2019.
http://hdl.handle.net/1802/14773.
MLA Handbook (7th Edition):
Evans, Meagan Elizabeth (1981 - ). “I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile.” 2011. Web. 08 Dec 2019.
Vancouver:
Evans ME(-). I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile. [Internet] [Doctoral dissertation]. University of Rochester; 2011. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1802/14773.
Council of Science Editors:
Evans ME(-). I. Energetics of C–H bond activation of functionalized
hydrocarbons. II. C–H and C–CN bond activation of acetonitrile and
benzonitrile. [Doctoral Dissertation]. University of Rochester; 2011. Available from: http://hdl.handle.net/1802/14773
Queens University
9.
Zhao, Yigang.
Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
.
Degree: Chemistry, 2011, Queens University
URL: http://hdl.handle.net/1974/6671
► Chapter 2 of the thesis describes a highly efficient in situ method for the reduction of amides to aldehydes and aryl O-carbamates to phenols and…
(more)
▼ Chapter 2 of the thesis describes a highly efficient in situ method for the reduction of amides to aldehydes and aryl O-carbamates to phenols and other transformations involving hydrozirconations. The method, as a three-component-type reaction, involves in situ generation of the Schwartz reagent (Cp2Zr(H)Cl) from Cp2ZrCl2 and the reductant, LiAlH(O-t-Bu)3, and immediate reaction with a substrate. Substrates include aliphatic and aromatic tertiary amides which are reduced to aldehydes, aryl O-carbamates which are reduced to phenols, and alkynes which undergo other transformations via hydrozirconation. Compared to prior methods, this method has advantage in that reagents are inexpensive and stable, reaction times are short, and reaction temperatures are generally conveniently at room temperature. The use of the in situ method described herein instead of the requirement for the synthesis of the commercially available Schwartz reagent is estimated to provide more than 50% reduction in cost.
Chapter 3 of the thesis describes the discovery and development of efficient and regioselective Ru-catalyzed amide-directed C-H, C-N, C-O activation/C-C bond forming reactions, ester-directed C-O activation/C-C bond forming reaction, and amide-directed C-O activation/hydrodemethoxylation reactions under a simple RuH2(CO)(PPh3)3/toluene catalytic system. Of these, the amide-directed C-H activation/cross coupling reaction proceeds well but uniquely on furan 3-amide substrates while the ester-directed C-O activation is effective on the 2-MeO-1-naphthoic acid methyl ester. On the other hand, the amide-directed C-N and C-O activation/coupling reactions are broadly applicable on benzamides and naphthamides. All of these achievements of directed C-H, C-N, C-O activation/coupling reactions complement and may supercede the DoM (directed ortho metalation)-cross coupling strategy, and establish the catalytic base-free DoM-cross coupling process at non-cryogenic temperature as a convenient, economical and green alternative. The new catalytic amide-directed ortho-hydrodemethoxylation reaction has potential value in links to aromatic electrophilic substitution and DoM chemistries. Furthermore, a new borylation reaction via Ru-catalyzed amide-directed C-H activation/C-B bond forming process is also reported herein.
Subjects/Keywords: reduction; Schwartz reagent; amide; aldehyde;
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APA (6th Edition):
Zhao, Y. (2011). Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
. (Thesis). Queens University. Retrieved from http://hdl.handle.net/1974/6671
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Zhao, Yigang. “Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
.” 2011. Thesis, Queens University. Accessed December 08, 2019.
http://hdl.handle.net/1974/6671.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Zhao, Yigang. “Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
.” 2011. Web. 08 Dec 2019.
Vancouver:
Zhao Y. Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
. [Internet] [Thesis]. Queens University; 2011. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1974/6671.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Zhao Y. Reduction of Tertiary Benzamides to Benzaldehydes by an in situ-Generated Schwartz Reagent (Cp2Zr(H)Cl); Formal Synthesis of Lysergic Acid 2. Ru-Catalyzed Amide-Directed Aryl C-H, C-N and C-O Bond Functionalizations: C-B Formation, C-C Suzuki Cross Coupling and Hydrodemethoxylation
. [Thesis]. Queens University; 2011. Available from: http://hdl.handle.net/1974/6671
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Penn State University
10.
Lu, Chengxi.
Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides.
Degree: MS, Chemistry, 2012, Penn State University
URL: https://etda.libraries.psu.edu/catalog/21598
► A new Pd-catalyzed picolinamide-directed halogenation reaction of ortho-C(sp2)-H bonds is discussed. The usage of inexpensive inorganic salt (KBrO3, NaClO3/NaClO2 and KIO3) as halide source and…
(more)
▼ A new Pd-catalyzed picolinamide-directed halogenation
reaction of ortho-C(sp2)-H bonds is discussed. The usage of
inexpensive inorganic salt (KBrO3, NaClO3/NaClO2 and KIO3) as
halide source and K2S2O8 as oxidant offer a more practical method
to introduce halide atoms onto aromatic organic compound. This
method is effective on benzylamine picolinamides and arylethylamine
picolinamides.
Subjects/Keywords: Pd-catalyzed; C-H activation; Halogenation
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APA ·
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to Zotero / EndNote / Reference
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APA (6th Edition):
Lu, C. (2012). Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides. (Masters Thesis). Penn State University. Retrieved from https://etda.libraries.psu.edu/catalog/21598
Chicago Manual of Style (16th Edition):
Lu, Chengxi. “Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides.” 2012. Masters Thesis, Penn State University. Accessed December 08, 2019.
https://etda.libraries.psu.edu/catalog/21598.
MLA Handbook (7th Edition):
Lu, Chengxi. “Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides.” 2012. Web. 08 Dec 2019.
Vancouver:
Lu C. Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides. [Internet] [Masters thesis]. Penn State University; 2012. [cited 2019 Dec 08].
Available from: https://etda.libraries.psu.edu/catalog/21598.
Council of Science Editors:
Lu C. Palladium-catalyzed Halogenation Of Ortho-c-h Bonds Of
Benzylamine Picolinamides And Arylethylamine Picolinamides. [Masters Thesis]. Penn State University; 2012. Available from: https://etda.libraries.psu.edu/catalog/21598
University of California – Berkeley
11.
Tsai, Andy Siu-Chun.
Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis.
Degree: Chemistry, 2011, University of California – Berkeley
URL: http://www.escholarship.org/uc/item/23n227t9
► Chapter 1. A sequence of research projects beginning with studies in diastereoselective C-H bond functionalization applied to the synthesis of (-)-incarvaillateine to the Rh(III) catalyzed…
(more)
▼ Chapter 1. A sequence of research projects beginning with studies in diastereoselective C-H bond functionalization applied to the synthesis of (-)-incarvaillateine to the Rh(III) catalyzed arylation of imines, are described. Some theory and mechanistic considerations are discussed in relation to the genesis of these projects. Research directions are summarized and rationalized. Chapter 2. The synthesis of (-)-incarvillateine utilizing a key C-H bond alkylation step is described as a means to highlight the synthetic utility of a newly reported olefinic C-H bond functionalization methodology. Elements of diastereoselectivity are also explored in the key step which allows for the concise, stereoselective synthesis of the natural product. Progress in the area of enantioselective C-H alkylations are also summarized as it applies to the synthesis of other natural products. Chapter 3. A method for the enantioselective cyclization of N-allylimidazoles is developed. The reaction is thought to proceed via a novel, reactive N-heterocyclic carbene. High enantioselectivities are achieved, which is unusual in view of the elevated temperatures of the reaction.Chapter 4. The first general method for the oxidative coupling of unactivated alkenes via C-H bond functionalization is reported using a methyl oxime directing group. A silver abstractor is important to obtain reactivity. Several functional groups are compatible with the reaction and no precautions to exclude air are required.Chapter 5. A rare example of C-H activation and intermolecular coupling to N-protected-imines is achieved using a cationic Rh(III) catalyst. The reaction is directed by pyridines and related heterocycles and produces a variety of aryl-branched amines. The reaction accommodates several reactive functional groups and is mild enough to even couple with sensitive alkyl N-sulfonyl-imines.
Subjects/Keywords: Chemistry; catalysis; C-H activation; incarvillateine; rhodium
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APA (6th Edition):
Tsai, A. S. (2011). Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis. (Thesis). University of California – Berkeley. Retrieved from http://www.escholarship.org/uc/item/23n227t9
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Tsai, Andy Siu-Chun. “Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis.” 2011. Thesis, University of California – Berkeley. Accessed December 08, 2019.
http://www.escholarship.org/uc/item/23n227t9.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Tsai, Andy Siu-Chun. “Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis.” 2011. Web. 08 Dec 2019.
Vancouver:
Tsai AS. Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis. [Internet] [Thesis]. University of California – Berkeley; 2011. [cited 2019 Dec 08].
Available from: http://www.escholarship.org/uc/item/23n227t9.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Tsai AS. Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis. [Thesis]. University of California – Berkeley; 2011. Available from: http://www.escholarship.org/uc/item/23n227t9
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Manchester
12.
Eichler, Anja.
Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity.
Degree: 2016, University of Manchester
URL: http://www.manchester.ac.uk/escholar/uk-ac-man-scw:302167
► Catalytic, selective C-H bond activation for the oxidative hydroxylation RH → ROH of simple or complex compounds is of significant interest in synthetic organic chemistry.…
(more)
▼ Catalytic, selective C-H bond activation for the
oxidative hydroxylation RH → ROH of simple or complex compounds is
of significant interest in synthetic organic chemistry. One of the
major classes of enzymes used for C-H bond activation are
cytochrome P450 monooxygenases (EC 1.14.X.X), which can promote
chemo-, regio- and stereoselective oxidations under mild reaction
conditions. For the current study, catalytically self-sufficient
forms of biocatalyst P450cam-RhFRed were investigated. These
self-sufficient P450 systems were previously created by fusing the
reductase domain of P450 RhF (CYP116B2, RhFRed from Rhodococcus
sp.) with the catalytic domain of P450cam (CYP101A1, Pseudomonas
putida), thus mimicking the natural fusion of P450 RhF. The
generation of 93 P450cam-RhFRed variants has expanded the synthetic
toolbox to serve as a basis for exploring the substrate scope
towards ethylbenzenes, substituted alkylbenzenes, 4-ethylphenol and
(+)-pleuromutilin. To select for active mutants from this library
of 93, high throughput screening methods were developed. A pooling
approach was applied in order to express P450s and analyse them
against a panel of non-natural substrates, such as ethylbenzene,
4-ethylphenol and (+)-pleuromutilin in whole cell biotransformation
reactions. The concentration of P450 enzymes was determined using
CO difference spectroscopy in whole cells. The assay was
significantly improved both in terms of speed and safety by using
carbon monoxide releasing molecules as a source of CO rather than
the gas CO itself. These screening studies served as starting point
to identify P450cam-RhFRed mutants for specific reactions. In
particular, a systematic investigation of this library showed
mutants that generated chiral benzyl alcohols with good
enantioselectivities.To interpret these results on a structural
basis, molecular dynamics simulations were used to estimate
enantioselectivity of selected mutants for the regio-isomers of
methylated ethylbenzene derivatives. The results from the molecular
dynamics simulations were broadly consistent with experimentally
determined data and identified the importance of conformational
changes and flexibility of mutant-substrate complexes to enforce
enantioselectivity.
Catalytic, selective C-H bond activation for the
oxidative hydroxylation RH → ROH of simple or complex compounds is
of significant interest in synthetic organic chemistry. One of the
major classes of enzymes used for C-H bond activation are
cytochrome P450 monooxygenases (EC 1.14.X.X), which can promote
chemo-, regio- and stereoselective oxidations under mild reaction
conditions. For the current study, catalytically self-sufficient
forms of biocatalyst P450cam-RhFRed were investigated. These
self-sufficient P450 systems were previously created by fusing the
reductase domain of P450 RhF (CYP116B2, RhFRed from Rhodococcus
sp.) with the catalytic domain of P450cam (CYP101A1, Pseudomonas
putida), thus mimicking the natural fusion of P450 RhF. The
generation of 93 P450cam-RhFRed variants has expanded the…
Advisors/Committee Members: WEBB, SIMON SJ, Webb, Simon, Flitsch, Sabine.
Subjects/Keywords: C-H activation; P450 enzymes; Selectivity
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APA ·
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MLA ·
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Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Eichler, A. (2016). Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity. (Doctoral Dissertation). University of Manchester. Retrieved from http://www.manchester.ac.uk/escholar/uk-ac-man-scw:302167
Chicago Manual of Style (16th Edition):
Eichler, Anja. “Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity.” 2016. Doctoral Dissertation, University of Manchester. Accessed December 08, 2019.
http://www.manchester.ac.uk/escholar/uk-ac-man-scw:302167.
MLA Handbook (7th Edition):
Eichler, Anja. “Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity.” 2016. Web. 08 Dec 2019.
Vancouver:
Eichler A. Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity. [Internet] [Doctoral dissertation]. University of Manchester; 2016. [cited 2019 Dec 08].
Available from: http://www.manchester.ac.uk/escholar/uk-ac-man-scw:302167.
Council of Science Editors:
Eichler A. Investigations of Self-Sufficient P450cam Monooxygenases
for Activity and Enantioselectivity. [Doctoral Dissertation]. University of Manchester; 2016. Available from: http://www.manchester.ac.uk/escholar/uk-ac-man-scw:302167
Mississippi State University
13.
Reilly, Sean William.
Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.
Degree: PhD, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/
;
► <I>N</I>-Heterocyclic carbenes (NHCs) are one of the few ligand systems that can finely tune transition metal catalysts via sterics and electronics. The strong sigma-donating…
(more)
▼ <I>N</I>-Heterocyclic carbenes (NHCs) are one of the few ligand systems that can finely tune transition metal catalysts via sterics and electronics. The strong sigma-donating properties of these ancillary ligands allow the development of robust tridentate NHC pincer framework, which has emerged as an alternative to the phosphine pincer ligands. The combination of NHC and pincer systems has resulted in a new generation of catalytically active organometallic complexes reported throughout the literature.
CCC-NHC Rh pincer complexes were found to be catalytically active in
C-
C and
C-B bond formation via 1,4-addition reactions. In addition, the <I>in-situ</I> generated CCC-NHC Ir(H) pincer complex demonstrated catalytic activity in borylation of arene
C-H bonds. Preliminary results are comparable to the
C-H borylation results published by Hartwig and co-workers. The CCC-NHC Ir(H) pincer complex may also prove to be a suitable catalyst for alkane dehydrogenation, due to framework similarities of the highly active and durable PCP and POCOP pincer hydride systems.
Expansion of group 9 metal sources for transmetalation of the CCC-NHC Zr pincer complex afforded the development of CCC-NHC Rh(CO) and CCC-NHC Co complexes. Group 9 metal carbonyl complexes have been reported as active catalysts in photocatalytic
C-H
activation of small molecules. Testing of Co sources for transmetalation afforded three rare Co pincer complexes, and the first examples of CCC-NHC Co pincer complexes to date. Development of CCC-NHC pincer complexes with base metals provide cost-effect alternatives to pincer systems with precious metal centers, and is reported herein.
Advisors/Committee Members: Keith T. Mead (chair), Andrzej Sygula (committee member), Joesph P. Emerson (committee member), Edwin A. Lewis (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: C-H activation; pincer; NHC; carbene
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APA (6th Edition):
Reilly, S. W. (2015). Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;
Chicago Manual of Style (16th Edition):
Reilly, Sean William. “Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.” 2015. Doctoral Dissertation, Mississippi State University. Accessed December 08, 2019.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;.
MLA Handbook (7th Edition):
Reilly, Sean William. “Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.” 2015. Web. 08 Dec 2019.
Vancouver:
Reilly SW. Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. [Internet] [Doctoral dissertation]. Mississippi State University; 2015. [cited 2019 Dec 08].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;.
Council of Science Editors:
Reilly SW. Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. [Doctoral Dissertation]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;
North Carolina State University
14.
Foley, Nicholas Adam.
Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis.
Degree: PhD, Chemistry, 2009, North Carolina State University
URL: http://www.lib.ncsu.edu/resolver/1840.16/4976
► TpRu(CO)(NCMe)Ph catalyzes the addition of aromatic C-H bonds across double bonds (i.e., olefin hydroarylation). Second generation TpRu(L)(NCMe)R {L = PMe3, P(OCH2)3CEt or P(pyr)3; pyr =…
(more)
▼ TpRu(CO)(NCMe)Ph catalyzes the addition of aromatic
C-H bonds across double bonds (i.e., olefin hydroarylation). Second generation TpRu(L)(NCMe)R {L = PMe3, P(OCH2)3CEt or P(pyr)3; pyr = pyrollyl; R = Me or Ph} complexes were synthesized to compare olefin hydroarylation activity versus the parent CO analog (Chapters 2 through 4). Experimental and computational studies indicate that TpRu(L)(NCMe)Ph initiates ethylene hydrophenylation by dissociation of NCMe, coordination of ethylene, insertion of ethylene into the Ru-Ph bond, coordination of benzene and
C-H
activation of benzene to release the olefin hydroarylation product ethyl benzene. Previously, kinetic isotope effect studies indicated that the
C-H
activation step is the rate determining step for the overall catalytic cycle.
Kinetic studies indicate the stronger donating PMe3 and P(OCH2)3CEt ligands increase the rate of degenerate benzene
C-H
activation for TpRu(L)(NCMe)Ph systems relative to TpRu(CO)(NCMe)Ph. Hammett studies and kinetic isotope effect studies are consistent with a
C-H
activation mechanism which proceeds by a sigma-bond metathesis pathway. Increasing the acidity of the
C-H hydrogen, and the basicity of the ligand receiving the hydrogen, accelerates
C-H
activation.
In benzene and ethylene mixtures, TpRu(L)(NCMe)Ph systems have decreased catalytic activity for ethylene hydrophenylation with the PMe3 and P(OCH2)3CEt systems decomposing to TpRu(L)(ï ¨3-C4H7) analogs. Increased metal electron density raises the
activation barrier to olefin insertion allowing ethylene
C-H
activation to become competitive with ethylene insertion leading to TpRu(L)(ï ¨3-C4H7) formation. The P(pyr)3 ligand is electronically similar to CO, but its large steric bulk makes ethylene coordination endergonic, inhibiting entry into a catalytic ethylene hydrophenylation cycle.
In Chapter 5, TpRu(PMe3)(NCMe)Me stoichiometrically activates the sp3 bonds of acetonitrile, acetone and nitromethane to form TpRu(PMe3)(NCMe)CH2CN, TpRu(PMe3){κ2-O,N-OC(Me)
C(H)
C(Me)NH} and TpRu(PMe3){κ2-O,N-N(O)
C(H)(NO2)}, respectively. Experimental and computational studies suggest that
C-H
activation is promoted by thermodynamically favourable coordination via the heteroatomic functionality, increased basicity of the ligand receiving the hydrogen and substrate acidity. Additionally, TpRu(PMe3)(NCMe)Me mediates subsequent
C-
C/
C-N bond-forming reactions with acetonitrile and acetone.
In Chapter 6, a series of cationic [EpRu(L)(L’)R][A-] and [
C(pz)4Ru(L)(L’)R][A-] [Ep = tris(pyrazolyl)ethane; L = PMe3, P(OCH2)3CEt, or CO; L’ = PPh3, NCMe or THF; R = Me or Ph; A- = BAr’4, BPh4 or OTf; BAr’4 = {tetrakis(3,5-trifluoromethyl)phenyl}borate; pz = pyrazolyl] complexes were synthesized and tested for olefin hydroarylation activity. [EpRu(CO)(NCMe)Ph][A-] (A- = BAr’4 or BPh4) was found to catalyze a 2 – 3 turnovers of ethyl benzene in ethylene and benzene mixtures. Cyclic voltammetry gave strongly positive irreversible oxidative potentials suggesting poor catalysis is linked to the…
Advisors/Committee Members: Dr. Mike H. Whangbo, Committee Member (advisor), Dr. Alexander Deiters, Committee Member (advisor), Dr. T. Brent Gunnoe, Committee Chair (advisor), Dr. James D. Martin, Committee Member (advisor).
Subjects/Keywords: Olefin Hydroarylation; C-H Activation; Ruthenium
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APA (6th Edition):
Foley, N. A. (2009). Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis. (Doctoral Dissertation). North Carolina State University. Retrieved from http://www.lib.ncsu.edu/resolver/1840.16/4976
Chicago Manual of Style (16th Edition):
Foley, Nicholas Adam. “Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis.” 2009. Doctoral Dissertation, North Carolina State University. Accessed December 08, 2019.
http://www.lib.ncsu.edu/resolver/1840.16/4976.
MLA Handbook (7th Edition):
Foley, Nicholas Adam. “Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis.” 2009. Web. 08 Dec 2019.
Vancouver:
Foley NA. Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis. [Internet] [Doctoral dissertation]. North Carolina State University; 2009. [cited 2019 Dec 08].
Available from: http://www.lib.ncsu.edu/resolver/1840.16/4976.
Council of Science Editors:
Foley NA. Synthesis and Comparative Studies of Ru(II) Complexes for Metal-mediated C-H Activation and Olefin Hydroarylation Catalysis. [Doctoral Dissertation]. North Carolina State University; 2009. Available from: http://www.lib.ncsu.edu/resolver/1840.16/4976
University of Rochester
15.
Grochowski, Matthew Robert (1975 - ).
Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides.
Degree: PhD, 2011, University of Rochester
URL: http://hdl.handle.net/1802/14122
► Reaction of (Cp*IrHCl)2 (Cp* = η5-C5Me5) with 2-methylthiophene and 2,5-dimethylthiophene at 120°C in the presence of H2 results in the cleavage of the thiophene carbon-sulfur…
(more)
▼ Reaction of (Cp*IrHCl)2 (Cp* = η5-C5Me5) with
2-methylthiophene and 2,5-dimethylthiophene at 120°C in the
presence of H2 results in the cleavage of the thiophene
carbon-sulfur bond(s). In both cases the thiophenes are ring opened
and hydrogenated resulting in dinuclear Ir complexes with bridging
thiolates. The primary product in the reaction involving
2.5-dimethylthiophene is [Cp*IrCl]2(μ-H)(μ-S-2-hexyl). This product
has been characterized and is present in diastereomeric pairs.
Reaction with 2-methylthiophene produces a complex mixture
consisting of five products. The product distribution consists of
mono and di-substituted bridging thiolate products three of which
have been structurally characterized by single-crystal X-ray
diffraction. Independent synthesis of each of these products has
been performed, and characterization of the reaction mixture has
been accomplished by 1H and 13C NMR spectroscopies, as well as by
ESI-MS and elemental analysis. Reaction with 2-acetylthiophene
showed very similar reactivity; an X-ray structure confirmed the
nature of the diastereomeric pairs present.
The processes of C–C
and C–S bond cleavage of 2-cyanothiophene have been studied with
the homogeneous organometallic compound [Ni(dippe)H]2. Reaction at
room temperature resulted in cleavage of the nitrile substituted
C–S bond to give the Ni-metallacycle complex
(dippe)Ni(K2-S,C–SCH=CHCH=C(CN)), which has been fully
characterized by NMR spectroscopy and X-ray diffraction. Conversion
to the C–CN cleavage product (dippe)Ni(CN)(2-thiophenyl) occurred
when the solution was heated to 85°C. On closer inspection four
other intermediates were observed by 31P NMR spectroscopy at -60°C.
Structures for the intermediates were elucidated through a
combination of independent synthesis, theoretical calculations,
chemical characterization, and experimental precedent. A kinetic
product (dippe)Ni(K2-S,C-SC(CN)=CHCH=CH) was formed from cleavage
of the non-substituted C–S bond, as well as a Ni(0) η2-nitrile
intermediate (dippe)Ni(η2-C,N-2-cyanothiophene), and a dinuclear
mixed Ni(0)-Ni(II) product.
The unusual lithium coordinated
complex [(dippe)Rh(μ-H)]2[LiBEt3H] was synthesized and
characterized by NMR spectroscopy and X-ray crystallography. The
[(dippe)Rh(μ-H)]2 and LiBEt3H moieties are bound together through
lithium. Bonding interactions occur between the lithium and the
metal hydrides, as well as the lithium and the B-H bond of BEt3H.
Formation of the complex is highly solvent dependent and may be
part of a general bonding phenomenon between borohydrides and metal
hydride complexes.
The rhodium dimer [Rh(dippe)(μ-H)]2 reacted
with 4-methyldibenzothiophene to form the C–S cleavage product
[Rh2(dippe)2(μ-S-MeC12H8)(μ-H)], which has been fully characterized
by NMR spectroscopy (1H, 31P, and 13C), elemental analysis,
APCI-MS, and X-ray diffraction. The crystal structure shows that
hydrogenolysis of the C-S bond occurs exclusively from the
unhindered side of 4-MeDBT. [Rh(dippe)(μ-H)]2 also reacts in an
analogous manner with…
Subjects/Keywords: HDS; C-S bond activation; Substituted thiophenes
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APA (6th Edition):
Grochowski, M. R. (. -. ). (2011). Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides. (Doctoral Dissertation). University of Rochester. Retrieved from http://hdl.handle.net/1802/14122
Chicago Manual of Style (16th Edition):
Grochowski, Matthew Robert (1975 - ). “Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides.” 2011. Doctoral Dissertation, University of Rochester. Accessed December 08, 2019.
http://hdl.handle.net/1802/14122.
MLA Handbook (7th Edition):
Grochowski, Matthew Robert (1975 - ). “Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides.” 2011. Web. 08 Dec 2019.
Vancouver:
Grochowski MR(-). Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides. [Internet] [Doctoral dissertation]. University of Rochester; 2011. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1802/14122.
Council of Science Editors:
Grochowski MR(-). Hydrodesulfurization modeling with iridium, rhodium, and
nickel hydrides. [Doctoral Dissertation]. University of Rochester; 2011. Available from: http://hdl.handle.net/1802/14122
University of Manchester
16.
Eichler, Anja.
Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity.
Degree: PhD, 2016, University of Manchester
URL: https://www.research.manchester.ac.uk/portal/en/theses/investigations-of-selfsufficient-p450cam-monooxygenases-for-activity-and-enantioselectivity(27df0fa8-b671-4593-8ec0-f993a31e120c).html
;
https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.728108
► Catalytic, selective C-H bond activation for the oxidative hydroxylation RH → ROH of simple or complex compounds is of significant interest in synthetic organic chemistry.…
(more)
▼ Catalytic, selective C-H bond activation for the oxidative hydroxylation RH → ROH of simple or complex compounds is of significant interest in synthetic organic chemistry. One of the major classes of enzymes used for C-H bond activation are cytochrome P450 monooxygenases (EC 1.14.X.X), which can promote chemo-, regio- and stereoselective oxidations under mild reaction conditions. For the current study, catalytically self-sufficient forms of biocatalyst P450cam-RhFRed were investigated. These self-sufficient P450 systems were previously created by fusing the reductase domain of P450 RhF (CYP116B2, RhFRed from Rhodococcus sp.) with the catalytic domain of P450cam (CYP101A1, Pseudomonas putida), thus mimicking the natural fusion of P450 RhF. The generation of 93 P450cam-RhFRed variants has expanded the synthetic toolbox to serve as a basis for exploring the substrate scope towards ethylbenzenes, substituted alkylbenzenes, 4-ethylphenol and (+)-pleuromutilin. To select for active mutants from this library of 93, high throughput screening methods were developed. A pooling approach was applied in order to express P450s and analyse them against a panel of non-natural substrates, such as ethylbenzene, 4-ethylphenol and (+)-pleuromutilin in whole cell biotransformation reactions. The concentration of P450 enzymes was determined using CO difference spectroscopy in whole cells. The assay was significantly improved both in terms of speed and safety by using carbon monoxide releasing molecules as a source of CO rather than the gas CO itself. These screening studies served as starting point to identify P450cam-RhFRed mutants for specific reactions. In particular, a systematic investigation of this library showed mutants that generated chiral benzyl alcohols with good enantioselectivities. To interpret these results on a structural basis, molecular dynamics simulations were used to estimate enantioselectivity of selected mutants for the regio-isomers of methylated ethylbenzene derivatives. The results from the molecular dynamics simulations were broadly consistent with experimentally determined data and identified the importance of conformational changes and flexibility of mutant-substrate complexes to enforce enantioselectivity.
Subjects/Keywords: 572; C-H activation; P450 enzymes; Selectivity
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APA (6th Edition):
Eichler, A. (2016). Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity. (Doctoral Dissertation). University of Manchester. Retrieved from https://www.research.manchester.ac.uk/portal/en/theses/investigations-of-selfsufficient-p450cam-monooxygenases-for-activity-and-enantioselectivity(27df0fa8-b671-4593-8ec0-f993a31e120c).html ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.728108
Chicago Manual of Style (16th Edition):
Eichler, Anja. “Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity.” 2016. Doctoral Dissertation, University of Manchester. Accessed December 08, 2019.
https://www.research.manchester.ac.uk/portal/en/theses/investigations-of-selfsufficient-p450cam-monooxygenases-for-activity-and-enantioselectivity(27df0fa8-b671-4593-8ec0-f993a31e120c).html ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.728108.
MLA Handbook (7th Edition):
Eichler, Anja. “Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity.” 2016. Web. 08 Dec 2019.
Vancouver:
Eichler A. Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity. [Internet] [Doctoral dissertation]. University of Manchester; 2016. [cited 2019 Dec 08].
Available from: https://www.research.manchester.ac.uk/portal/en/theses/investigations-of-selfsufficient-p450cam-monooxygenases-for-activity-and-enantioselectivity(27df0fa8-b671-4593-8ec0-f993a31e120c).html ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.728108.
Council of Science Editors:
Eichler A. Investigations of self-sufficient P450cam monooxygenases for activity and enantioselectivity. [Doctoral Dissertation]. University of Manchester; 2016. Available from: https://www.research.manchester.ac.uk/portal/en/theses/investigations-of-selfsufficient-p450cam-monooxygenases-for-activity-and-enantioselectivity(27df0fa8-b671-4593-8ec0-f993a31e120c).html ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.728108
University of Michigan
17.
Neufeldt, Sharon Rose.
Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization.
Degree: PhD, Chemistry, 2013, University of Michigan
URL: http://hdl.handle.net/2027.42/98061
► Because of their abundance, C-H bonds are highly attractive starting materials for the elaboration of complex molecules. Transition metal catalysis can enable these typically inert…
(more)
▼ Because of their abundance,
C-H bonds are highly attractive starting materials for the elaboration of complex molecules. Transition metal catalysis can enable these typically inert bonds to undergo functionalization via a metal-catalyzed
C-H
activation step. In particular, ligand-directed PdII/PdIV-catalyzed
C-H functionalization reactions have emerged as powerful techniques for diverse bond constructions. Nevertheless, these methodologies face a number of challenges that limit their applicability. These challenges include the common requirement for harsh reaction conditions, the shortage of examples of asymmetric functionalization reactions, and the poor transformability of most directing groups. This thesis describes the development of new methodologies that aim to address these challenges.
Chapter 2 describes a new photoredox Pd/Ir-catalyzed
C-H arylation reaction that reroutes the mechanism of Pd-catalyzed
C-H arylation with diaryliodonium salts from an ionic pathway through a radical-mediated pathway. This radical-mediated transformation proceeds at room temperature in a non-acidic solvent, conditions that are considerably milder than those required for
C-H arylation with diaryliodonium salts via a traditional PdII/PdIV mechanism (100 ºC in acetic acid).
Chapter 3 details the development of a Pd-catalyzed
C-H alkylation reaction that utilizes convenient potassium alkyltrifluoroborate salts in combination with a 1 e- oxidant (MnIII). Several pieces of evidence support an alkyl radical-mediated mechanism for this transformation. The alkylation reaction requires only mild temperatures (25-40 ºC), in contrast to the significantly higher temperatures (70-110 ºC) needed for previous examples of analogous transformations.
Chapter 4 describes efforts toward understanding the interplay of chiral directing groups with Pd in the context of high oxidation state Pd catalysis. In this work, we developed a chiral ligand-directed Pd-catalyzed asymmetric alkene dioxygenation reaction.
Chapter 5 describes the identification of a transformable directing ligand for Pd-catalyzed
C-H functionalization reactions. In situ generated O-acetyl oxime ethers were shown to be effective directing groups that are stable under the reaction conditions required for Pd-catalyzed
C-H oxygenation, but can then be readily manipulated to afford ketones, alcohols, amines, and heterocycles.
Advisors/Committee Members: Sanford, Melanie (committee member), Savage, Phillip E. (committee member), McNeil, Anne Jennifer (committee member), Montgomery, John (committee member).
Subjects/Keywords: Palladium; C-H Activation; Radicals; Chemistry; Science
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APA (6th Edition):
Neufeldt, S. R. (2013). Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization. (Doctoral Dissertation). University of Michigan. Retrieved from http://hdl.handle.net/2027.42/98061
Chicago Manual of Style (16th Edition):
Neufeldt, Sharon Rose. “Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization.” 2013. Doctoral Dissertation, University of Michigan. Accessed December 08, 2019.
http://hdl.handle.net/2027.42/98061.
MLA Handbook (7th Edition):
Neufeldt, Sharon Rose. “Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization.” 2013. Web. 08 Dec 2019.
Vancouver:
Neufeldt SR. Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization. [Internet] [Doctoral dissertation]. University of Michigan; 2013. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/2027.42/98061.
Council of Science Editors:
Neufeldt SR. Palladium-Catalyzed Ligand-Directed C-H and C=C Bond Functionalization. [Doctoral Dissertation]. University of Michigan; 2013. Available from: http://hdl.handle.net/2027.42/98061
University of Edinburgh
18.
Cant, Alastair Alexander.
Investigations into aryne chemistry.
Degree: PhD, 2012, University of Edinburgh
URL: http://hdl.handle.net/1842/6249
► The first project in this thesis describes our research reacting arynes with tertiary allyl amines to generate functionalised anilines via a benzyne induced aza-Claisen reaction.…
(more)
▼ The first project in this thesis describes our research reacting arynes with tertiary allyl amines to generate functionalised anilines via a benzyne induced aza-Claisen reaction. This process works in good to excellent yields and the methodology can be further applied to make benzannulated medium sized ring amine systems. The second project covered in this thesis details our studies in the generation of benzyne from benzoic acid. This process utilises palladium catalysis involving an ortho C-H activation of benzoic acid which generates a 5 membered palladacycle. This palladacycle then spontaneously decomposes with heat to generate palladium bound benzyne and carbon dioxide. The yield of benzyne was monitored by observing the amount of triphenylene formed in the process. Further synthetic applications in this process were limited, but it was shown that the benzyne could be reacted with alkynes to generate phenanthrene and naphthalene products. The
third project in this thesis details our work on the insertion of benzyne into the C–S bond of thioesters. Using palladium catalysis and an o-trimethylsilylphenyl triflate benzyne precursor, a variety of thioethers were produced. The yields for this reaction were moderate to good but it was found that only aromatic substituents were tolerated on the thioester.
Subjects/Keywords: 547.6; benzyne; arynes; C-H activation
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APA (6th Edition):
Cant, A. A. (2012). Investigations into aryne chemistry. (Doctoral Dissertation). University of Edinburgh. Retrieved from http://hdl.handle.net/1842/6249
Chicago Manual of Style (16th Edition):
Cant, Alastair Alexander. “Investigations into aryne chemistry.” 2012. Doctoral Dissertation, University of Edinburgh. Accessed December 08, 2019.
http://hdl.handle.net/1842/6249.
MLA Handbook (7th Edition):
Cant, Alastair Alexander. “Investigations into aryne chemistry.” 2012. Web. 08 Dec 2019.
Vancouver:
Cant AA. Investigations into aryne chemistry. [Internet] [Doctoral dissertation]. University of Edinburgh; 2012. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1842/6249.
Council of Science Editors:
Cant AA. Investigations into aryne chemistry. [Doctoral Dissertation]. University of Edinburgh; 2012. Available from: http://hdl.handle.net/1842/6249
Princeton University
19.
Boaz, Nicholas Charles.
The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
.
Degree: PhD, 2015, Princeton University
URL: http://arks.princeton.edu/ark:/88435/dsp01ks65hf52g
► The unactivated C-H bonds of hydrocarbons are some of the most common chemical functionalities in organic molecules. Despite their ubiquity, they are some of the…
(more)
▼ The unactivated
C-H bonds of hydrocarbons are some of the most common chemical functionalities in organic molecules. Despite their ubiquity, they are some of the most difficult functional groups to manipulate because of their kinetic inertness, stemming from the strong non-polar
C-H bond. The focus of this work is the development and mechanistic study of processes that break strong
C-H bonds in a selective manner.
Sulfonated oxoFeIV porphyrins (models of the compound II state of CYP) are shown to be basic with measureable pKa values. This measured pKa represents a novel two-proton electromeric equilibrium between oxoFeIV porphyrin and the corresponding (OH2)2FeIII porphyrin cation radicals. The nature of this equilibrium, in combination with the empirical observation of both substrate and solvent-derived deuterium kinetic isotope effects, indicates a new mode of
C-H bond scission. The solvent-proton-assisted, proton-coupled electron transfer proposed leads to a net increase in the thermodynamic driving force of
C-H cleavage when compared to a single proton model. An extension of this work shows that sulfonated iron porphyrins were shown to have oxidation behavior, which was highly dependant upon both the electronics of the porphyrin ring and the novel two-proton pKa.
The mechanism of a reaction system that utilizes combinations of high-valent iodine oxides and catalytic amounts of chloride to selectively oxidize methane was determined to function via a radical pathway. Mechanistic studies suggest a catalytic cycle where alkyl radicals generated by hydrogen atom abstraction from chlorine atoms are able to react with iodine generated in situ. The transiently formed alkyl iodide then undergoes solvolysis to yield the product ester. This process of radical based
C-H ester formation is extended to substrates containing benzylic
C-H bonds by replacing the catalyst with the well-studied N-oxyl catalyst N-hydroxyphthalimide (NHPI). This NHPI-iodate system was shown to be effective in the functionalization of primary and secondary benzylic
C-H bonds in moderate to good yield.
Advisors/Committee Members: Groves, John T (advisor).
Subjects/Keywords: C-H Activation;
Heme;
Iodine;
Iron;
Methane
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APA (6th Edition):
Boaz, N. C. (2015). The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
. (Doctoral Dissertation). Princeton University. Retrieved from http://arks.princeton.edu/ark:/88435/dsp01ks65hf52g
Chicago Manual of Style (16th Edition):
Boaz, Nicholas Charles. “The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
.” 2015. Doctoral Dissertation, Princeton University. Accessed December 08, 2019.
http://arks.princeton.edu/ark:/88435/dsp01ks65hf52g.
MLA Handbook (7th Edition):
Boaz, Nicholas Charles. “The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
.” 2015. Web. 08 Dec 2019.
Vancouver:
Boaz NC. The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
. [Internet] [Doctoral dissertation]. Princeton University; 2015. [cited 2019 Dec 08].
Available from: http://arks.princeton.edu/ark:/88435/dsp01ks65hf52g.
Council of Science Editors:
Boaz NC. The Development and Study of Practical C-H Functionalization Reactions Using Mechanistic Tools
. [Doctoral Dissertation]. Princeton University; 2015. Available from: http://arks.princeton.edu/ark:/88435/dsp01ks65hf52g
University of Rochester
20.
Li, Ting (1982 - ); Jones, William D.; Ateşin, Tülay Aygan (1976 - ).
Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel.
Degree: PhD, 2011, University of Rochester
URL: http://hdl.handle.net/1802/14156
► [Ni(dippe)H]2 complex has been reacted with a variety of carbon nitriles. Upon mixing with substrates, it releases H2 to generate the 14-electron fragment [Ni(dippe)], which…
(more)
▼ [Ni(dippe)H]2 complex has been reacted with a
variety of carbon nitriles. Upon mixing with substrates, it
releases H2 to generate the 14-electron fragment [Ni(dippe)], which
is proposed to be the active species in bond activations.
In the
reaction with acetonitrile, initially the η2-nitrile complex was
observed, which upon heating or photolysis leads to the C-CN bond
activation product Ni(dippe)(CH3)(CN). No product from C-H bond
cleavage was seen and the independently synthesized
Ni(dippe)(H)(CH2CN) complex was very unstable and can only exist at
low temperature. Computational studies using DFT calculation
methods showed that the C-CN bond activation is favored exclusively
over the C-H bond activation due to the strong thermodynamic
driving force and slightly lower kinetic barrier.
In reactions
with aromatic nitriles, the [Ni(dippe)] fragment first coordinates
η2 to the nitrile C≡N and/or C=C moiety. Rearrangement then occurs
to give the C–CN oxidative addition product Ni(dippe)(Aryl)(CN).
Both experimental and DFT calculation results have shown that an
η2-arene complex with nickel coordinated to the C=C double bond
next to the cyano substituent is the crucial intermediate leading
to C–CN bond activation. Furthermore, the fluxional processes of
the η2-arene species were investigated by low-temperature
experiments as well as computational methods. In the cases of
benzonitrile and dicyanobenzenes, a mechanism was found with the
Ni(dippe) fragment rotating as it migrates around the phenyl ring
through a series of η3-allyl-like transition states. For polycyclic
aromatic nitriles, only certain η2-arenes were stable enough to
contribute to the fluxional process, and nickel migrates via an
η4-coordinated transition state. The transition states connecting
the η2-nitrile complex to the η2-arene intermediate and the
η2-arene intermediate to the C–CN bond activation products are at
much higher energies compared to those for migration around the
ring. In the reaction of 9-cyanoanthracene, the instability of the
η2-arene precursor and the high energy activation barrier resulted
in the absence of the C–CN oxidative addition product. The complex
with 9-cyanophenanthrene only undergoes C–CN cleavage upon
photolysis. The Lewis acid BEt3 disfavors the C-CN bond activation
in acetonitrile, but can facilitate C-CN cleavage in aromatic
nitriles.
The isomerization of 2-methyl-3-butenenitrile (2M3BN)
carried out by [Ni(dippe)H]2 can follow either a C-CN activation
pathway to form the linear product 3-pentenenitrile (3PN), or a C-H
activation pathway to give the branched olefin product
2-methyl-2-butenenitrile (2M2BN). Both pathways have been studied
by DFT calculation methods and the results matched well with those
observed in stoichiometric experiments. A detailed mechanism has
been proposed and tested on several other model bisphosphine
ligands to investigate bite angle and electronic effects on the
selectivity of nickel bisphosphine catalysts.
In the reaction of
[Ni(dippe)H]2 with 2-cyanothiophene, the processes of C–C and C–S…
Subjects/Keywords: C-C bond activation; DFT calculation; Nickel; Bisphosphine ligands
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APA ·
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MLA ·
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Manager
APA (6th Edition):
Li, Ting (1982 - ); Jones, William D.; Ateşin, T. A. (. -. ). (2011). Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel. (Doctoral Dissertation). University of Rochester. Retrieved from http://hdl.handle.net/1802/14156
Chicago Manual of Style (16th Edition):
Li, Ting (1982 - ); Jones, William D.; Ateşin, Tülay Aygan (1976 - ). “Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel.” 2011. Doctoral Dissertation, University of Rochester. Accessed December 08, 2019.
http://hdl.handle.net/1802/14156.
MLA Handbook (7th Edition):
Li, Ting (1982 - ); Jones, William D.; Ateşin, Tülay Aygan (1976 - ). “Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel.” 2011. Web. 08 Dec 2019.
Vancouver:
Li, Ting (1982 - ); Jones, William D.; Ateşin TA(-). Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel. [Internet] [Doctoral dissertation]. University of Rochester; 2011. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1802/14156.
Council of Science Editors:
Li, Ting (1982 - ); Jones, William D.; Ateşin TA(-). Experimental and theoretical investigations of C-C, C-H
and C-S bond activations of nitriles using zerovalent
nickel. [Doctoral Dissertation]. University of Rochester; 2011. Available from: http://hdl.handle.net/1802/14156
University of California – Berkeley
21.
Leger, Paul Robert.
Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products.
Degree: Chemistry, 2016, University of California – Berkeley
URL: http://www.escholarship.org/uc/item/9dw4s8f7
► This dissertation describes our efforts toward the total synthesis of complex natural products in the Lycopodium alkaloid and phomactin terpenoid families. The first chapter focuses…
(more)
▼ This dissertation describes our efforts toward the total synthesis of complex natural products in the Lycopodium alkaloid and phomactin terpenoid families. The first chapter focuses on our strategy to construct fawcettimine-type Lycopodium alkaloids (such as palhinine A) that contain unique bridging ring systems. The synthesis of a model substrate to examine an atom- transfer radical cyclization is described, as well as the synthesis of a 6-5-9 tricycle that could serve as a common intermediate to access many fawcettimine-type natural products.After observing an unprecedented hydroamination while working toward the synthesis of Lycopodium alkaloids, we explored the possibility that trimethylsilyl iodide (TMSI) could be a novel effector of this transformation. The second chapter describes our optimization studies of this hydroamination reaction on simple sulfonamides. We show that catalytic amounts of TMSI and water are unique in their ability to effect hydroamination and hydroetherification of unactivated olefins at room temperature. We found that the iodide anion is crucial to obtain high reactivity at low temperatures.The third chapter of this dissertation provides background and initial strategies toward the synthesis of phomactin natural products. Biological activity and previous syntheses are described. Our general strategy for accessing the phomactin terpenoids by utilizing strategic C–C activation of a cyclobutanol-derived substrate is illustrated as well as initial strategies and model studies. These include investigating C(sp3)–H functionalization reactions with a ketone-derived directing group and assessing the ability to accomplish a hydrazine/aldehyde “traceless” bond construction.The fourth chapter describes the development of our synthetic route to access several phomactin-like compounds. This has been accomplished through exploiting the unique properties of cyclobutanol-containing compounds. Both π-allyl cross-coupling and aldehyde addition reactions are efficient means of appending the linear fragment to the [3.1.1]bicycle. Templated macrocyclization was achieved in excellent yield, aided by the scaffolding ability of the rigid [3.1.1]bicycle. The cyclobutanol was selectively cleaved open through the action of rhodium catalysis. We’ve shown mechanistically that the products of this process are dependent on subtle changes to the substrate as well as the solvent. Final functionalizations include a reductive sulfone removal in the presence of an enone moiety via the intermediacy of an in situ generated cyclopropanol “protecting group”.
Subjects/Keywords: Chemistry; C-C activation; hydroamination; Lycopodium; natural products; phomactin; total synthesis
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APA (6th Edition):
Leger, P. R. (2016). Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products. (Thesis). University of California – Berkeley. Retrieved from http://www.escholarship.org/uc/item/9dw4s8f7
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Leger, Paul Robert. “Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products.” 2016. Thesis, University of California – Berkeley. Accessed December 08, 2019.
http://www.escholarship.org/uc/item/9dw4s8f7.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Leger, Paul Robert. “Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products.” 2016. Web. 08 Dec 2019.
Vancouver:
Leger PR. Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products. [Internet] [Thesis]. University of California – Berkeley; 2016. [cited 2019 Dec 08].
Available from: http://www.escholarship.org/uc/item/9dw4s8f7.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Leger PR. Hydroamination and C–C Activation Methods for the Expedient Synthesis of Lycopodium Alkaloids and Phomactin Natural Products. [Thesis]. University of California – Berkeley; 2016. Available from: http://www.escholarship.org/uc/item/9dw4s8f7
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Texas – Austin
22.
Ren, Zhi.
Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy.
Degree: PhD, Chemistry, 2016, University of Texas – Austin
URL: http://hdl.handle.net/2152/39758
► Transition metal catalyzed functionalization of carbon-hydrogen bonds (C−H bonds) has become an exponentially growing field. Particularly, Pd-catalyzed methods with various directing groups (DGs) have been…
(more)
▼ Transition metal catalyzed functionalization of carbon-hydrogen bonds (C−H bonds) has become an exponentially growing field. Particularly, Pd-catalyzed methods with various directing groups (DGs) have been developed for site selectivity. In addition, the use of an oxime as a DG proved to be an efficient and removable DG. However, alcohol-based directing strategies are still rare and underdeveloped. The research and development in this dissertation mainly focused on the utilization of masked alcohols as DGs for late stage diversification. With an exo-directing strategy, the syntheses of chemically differentiated vicinal diols and 2-hydroxyalkylphenol derivatives were achieved. Through a series of studies on cyclopalladation of methine groups, the first direct C−H
activation complex was prepared and characterized. Additionally, a comprehensive introduction of TM-catalyzed alkylation of aromatic C−H bonds with simple olefins was illustrated.
Advisors/Committee Members: Dong, Guangbin (advisor), Krische, Michael J. (committee member), Anslyn, Eric V. (committee member), Rose, Michael J. (committee member), Liu, Hung-Wen (Ben) (committee member).
Subjects/Keywords: C-H activation; C-H functionalization; Palladium catalysis
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APA (6th Edition):
Ren, Z. (2016). Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy. (Doctoral Dissertation). University of Texas – Austin. Retrieved from http://hdl.handle.net/2152/39758
Chicago Manual of Style (16th Edition):
Ren, Zhi. “Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy.” 2016. Doctoral Dissertation, University of Texas – Austin. Accessed December 08, 2019.
http://hdl.handle.net/2152/39758.
MLA Handbook (7th Edition):
Ren, Zhi. “Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy.” 2016. Web. 08 Dec 2019.
Vancouver:
Ren Z. Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy. [Internet] [Doctoral dissertation]. University of Texas – Austin; 2016. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/2152/39758.
Council of Science Editors:
Ren Z. Palladium-catalyzed carbon-hydrogen bond functionalization utilizing an exo-directing strategy. [Doctoral Dissertation]. University of Texas – Austin; 2016. Available from: http://hdl.handle.net/2152/39758
23.
Pierre, Cathleen.
Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation.
Degree: Docteur es, Chimie organique, 2012, Université Claude Bernard – Lyon I
URL: http://www.theses.fr/2012LYO10207
► La synthèse de produits complexes se doit de prendre en compte de nouvelles méthodes desynthèse plus efficaces, dont la fonctionnalisation de liaisons carbone-hydrogène. Dans cecontexte,…
(more)
▼ La synthèse de produits complexes se doit de prendre en compte de nouvelles méthodes desynthèse plus efficaces, dont la fonctionnalisation de liaisons carbone-hydrogène. Dans cecontexte, la catalyse homogène par les métaux de transition s’est avérée performante, tout encontrôlant la régio- et la chimiosélectivité de la réaction. Les travaux de thèse présentés dansce manuscrit témoignent de l’efficacité de cette stratégie pour la construction rapide decomplexité moléculaire.Dans un premier temps, nous nous sommes intéressés à l’utilisation de précurseurs chlorés, cequi a permis d’étendre significativement le champ d’application de l’arylation C(sp3)-Hintramoléculaire pallado-catalysée. Ces travaux ont conduit à la synthèse de nombreuxhétérocycles, difficilement accessibles par d’autres voies de synthèse plus traditionnelles.Dans un deuxième temps, le développement d’une méthodologie de double arylation C-Hnous a permis de synthétiser des molécules polycycliques aux squelettes originaux. Une seuleet même espèce catalytique permet dans ce cas de réaliser les deux opérations d’activation CHavec succès.Par la suite, nous avons montré qu’il était possible de synthétiser des composés énantioenrichispar arylation C(sp3)-H intramoléculaire asymétrique. Pour cela, les ligands chiraux detype phosphépine se sont avérés particulièrement performants, et induisent desénantiosélectivités prometteuses.Enfin, notre attention s’est portée vers la synthèse de polycycles par arylation C(sp3)-Hintramoléculaire deshydrogénante. Les résultats encourageants obtenus apparaissent commeune preuve de concept dans ce domaine, où très peu de travaux de recherche ont été rapportés.
The direct functionalization of C-H bonds constitutes a faster and more « atom-economical »synthetic approach. This concept is gradually modifying organic chemistry, because itprovides chemists of both academic and industrial worlds with new disconnection strategies,giving access to molecules of original structures and properties in a more efficient andecological manner.In this context, we first investigated the extension of the intramolecular palladium-catalyzedC(sp3)-H arylation, by using aryl chlorides as coupling partners. This methodology wasapplied to the synthesis of fused valuable five-membered carbocycles and heterocycles.A further part of this work focused on the synthesis of polycyclic molecules by double C-Harylations. Interestingly, a single batch of catalyst was able to perform both operations in onepot, which indicates that this concept can be used for the rapid construction of molecularcomplexity.Then, we focused our efforts on the enantioselective synthesis of indanes and heterocyclicanalogues by intramolecular C(sp3)-H arylation. The employment of a chiral binepine ligandplays a key role in this palladium-catalyzed process to achieve moderate to highstereoinduction.Finally, our work was devoted to the construction of fused thiophenes by intramolecular PdIIcatalyzeddeshydrogenative C(sp3)–H arylation.
Advisors/Committee Members: Baudoin, Olivier (thesis director).
Subjects/Keywords: Fonctionnalisation C-H; Activation C-H; Arylation C-H; Catalyse organométallique; Chloroarènes; Benzocyclobutènes; Activation C-H asymétrique; Palladium; C-H functionalization; C-H activation; C-H arylation; Organometallic catalysis; Chloroarenes; Benzocyclobutenes; Asymmetric C-H activation; Palladium; 541.395
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APA (6th Edition):
Pierre, C. (2012). Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation. (Doctoral Dissertation). Université Claude Bernard – Lyon I. Retrieved from http://www.theses.fr/2012LYO10207
Chicago Manual of Style (16th Edition):
Pierre, Cathleen. “Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation.” 2012. Doctoral Dissertation, Université Claude Bernard – Lyon I. Accessed December 08, 2019.
http://www.theses.fr/2012LYO10207.
MLA Handbook (7th Edition):
Pierre, Cathleen. “Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation.” 2012. Web. 08 Dec 2019.
Vancouver:
Pierre C. Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation. [Internet] [Doctoral dissertation]. Université Claude Bernard – Lyon I; 2012. [cited 2019 Dec 08].
Available from: http://www.theses.fr/2012LYO10207.
Council of Science Editors:
Pierre C. Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium : synthesis of polycyclic molecules by intramolecular palladium-catalyzed C(sp³)-H arylation. [Doctoral Dissertation]. Université Claude Bernard – Lyon I; 2012. Available from: http://www.theses.fr/2012LYO10207
Princeton University
24.
Nielsen, Daniel.
Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
.
Degree: PhD, 2013, Princeton University
URL: http://arks.princeton.edu/ark:/88435/dsp01ww72bb577
► Epoxides and aziridines are invaluable substrates for complex molecule synthesis due to their accessibility and proclivity toward ring opening. Generally, C-C bond formation with these…
(more)
▼ Epoxides and aziridines are invaluable substrates for complex molecule synthesis due to their accessibility and proclivity toward ring opening. Generally,
C-
C bond formation with these substrates is uncatalyzed and requires either harsh stoichiometric organometallic reagents or a narrow set of stabilized carbanions, thereby limiting the generality of these transformations. To address these drawbacks, we have investigated the transition metal-catalyzed cross coupling of epoxides and aziridines. Conditions for the coupling of styrenyl epoxides with boronic acids were developed; a variety of alpha-substituted alcohols are generated with good reaction efficiency. Mechanistic studies support a multi-catalytic sequence involving Csp3-O bond
activation. This methodology was extended to include the cross coupling of simple aliphatic aziridines with zinc nucleophiles. Crucial to the success of this transformation was the development of a novel protecting group capable of coordinating the catalyst, activating the aziridine toward oxidative addition, and assisting in reductive elimination. This transformation represents the first use of a non-benzylic or allylic Csp3-N bond as an electrophile in a catalytic cross-coupling reaction and affords medicinally relevant beta-substituted amines.
Advisors/Committee Members: Doyle, Abigail G (advisor).
Subjects/Keywords: aziridine;
C-N bond activation;
C-O bond activation;
cross coupling;
epoxide
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APA (6th Edition):
Nielsen, D. (2013). Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
. (Doctoral Dissertation). Princeton University. Retrieved from http://arks.princeton.edu/ark:/88435/dsp01ww72bb577
Chicago Manual of Style (16th Edition):
Nielsen, Daniel. “Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
.” 2013. Doctoral Dissertation, Princeton University. Accessed December 08, 2019.
http://arks.princeton.edu/ark:/88435/dsp01ww72bb577.
MLA Handbook (7th Edition):
Nielsen, Daniel. “Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
.” 2013. Web. 08 Dec 2019.
Vancouver:
Nielsen D. Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
. [Internet] [Doctoral dissertation]. Princeton University; 2013. [cited 2019 Dec 08].
Available from: http://arks.princeton.edu/ark:/88435/dsp01ww72bb577.
Council of Science Editors:
Nielsen D. Activation of Carbon-Heteroatom Bonds: Transition Metal-Catalyzed Coupling of Strained Rings
. [Doctoral Dissertation]. Princeton University; 2013. Available from: http://arks.princeton.edu/ark:/88435/dsp01ww72bb577
25.
Palazzolo, Alberto.
Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques.
Degree: Docteur es, Chimie, 2019, Paris Saclay
URL: http://www.theses.fr/2019SACLS276
► Les composés marqués aux isotopes de l’hydrogène possèdent des nombreuses applications lors des phases précliniques de développement des médicaments. Par exemple, les composés deutérés sont…
(more)
▼ Les composés marqués aux isotopes de l’hydrogène possèdent des nombreuses applications lors des phases précliniques de développement des médicaments. Par exemple, les composés deutérés sont utilisés comme étalons internes dans la quantification par LC-MS de métabolites alors que les molécules tritiées sont souvent des radiotraceurs de choix dans les études d’absorption, distribution, métabolisme et excrétion (ADME) moléculaire des candidats médicaments. Après une brève introduction, un premier chapitre discutera du développement d’une méthode douce et sélective, catalysée par des nanoparticules de ruthénium, qui permet d’effectuer le marquage en une étape de bases azotées et de médicaments dérivés. En changeant le ligand qui stabilise le nanocatalyseur, on a réalisé des échanges isotopiques compliqués tels que des tritiations en utilisant une pression sous-atmosphérique de tritium gaz et des deutérations d’oligonucleotides sensibles. Le chapitre suivant décrira la modification des catalyseurs commerciaux à base de ruthénium grâce à la coordination de carbènes N-hétérocycliques (NHCs). La modification assure une régio- et une chimiosélectivité améliorées lors de la deutération d’alcools aliphatiques. Certains des catalyseurs modifiés ont permis l’échange hydrogène/deutérium sur des molécules, particulièrement sensibles à la réduction, qui n’ont pas pu être isolées en utilisant le catalyseur commercial. Dans le dernier chapitre, la synthèse et l’évaluation de l’activité catalytique des nanoparticules à base d’iridium seront discutées. Ces nanocatalyseurs ont démontré une réactivité intéressante dans le marquage des composés complexes. Dans certains cas, les nanoparticules d’iridium ont permis l’incorporation de deutérium sur des positions inhabituelles en comparaison avec d’autres réactions d’échange isotopique déjà décrites.
Hydrogen isotopes labelled compounds possess a broad range of application in the early pre-clinical phases of drug development process. For instance, deuterated compounds are applied as internal standard in quantitative LC-MS techniques while tritiated molecules are often the preferred radioactive tracers for the study of molecular absorption, distribution, metabolism and excretion (ADME). After a brief introduction, a first chapter will discuss the development of a mild and selective method to perform late stage labelling of variously functionalized nucleobases and drug analogues catalyzed by ruthenium nanoparticles. By changing the ligand which stabilizes the nanocatalyst, we achieved challenging isotopic exchanges such as tritiations of pharmaceuticals using subatmospheric pressure of tritium gas and deuteration of sensible oligonucleotides. The next chapter will describe the modification of commercially available ruthenium nanocatalysts via the coordination of N-Heterocyclic carbenes (NHCs). The modification granted enhanced regio and chemoselectivity for the deuteration of aliphatic alcohols. Some of the modified ruthenium catalysts allowed the hydrogen/deuterium exchange on easily…
Advisors/Committee Members: Pieters, Grégory (thesis director).
Subjects/Keywords: Deuteration; Tritiation; C-H activation; Radiochimie; Deuteration; Tritiation; C-H activation; Radiochemistry
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APA ·
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APA (6th Edition):
Palazzolo, A. (2019). Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques. (Doctoral Dissertation). Paris Saclay. Retrieved from http://www.theses.fr/2019SACLS276
Chicago Manual of Style (16th Edition):
Palazzolo, Alberto. “Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques.” 2019. Doctoral Dissertation, Paris Saclay. Accessed December 08, 2019.
http://www.theses.fr/2019SACLS276.
MLA Handbook (7th Edition):
Palazzolo, Alberto. “Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques.” 2019. Web. 08 Dec 2019.
Vancouver:
Palazzolo A. Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques. [Internet] [Doctoral dissertation]. Paris Saclay; 2019. [cited 2019 Dec 08].
Available from: http://www.theses.fr/2019SACLS276.
Council of Science Editors:
Palazzolo A. Development of new methods for the hydrogen isotope exchange catalyzed by metallic nanoparticles : Développement des nouvelles méthodes pour l’hydrogène isotope exchange catalysé par des nanoparticules métalliques. [Doctoral Dissertation]. Paris Saclay; 2019. Available from: http://www.theses.fr/2019SACLS276
Universitat de Girona
26.
Planas Fàbrega, Oriol.
Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies.
Degree: Departament de Química, 2018, Universitat de Girona
URL: http://hdl.handle.net/10803/482111
► L’objectiu principal d’aquesta tesi doctoral és la síntesis i la caracterització d’espècies organometàl•liques i estables aril-Co(III), fent ús de salts de cobalt(II) i d’un lligand…
(more)
▼ L’objectiu principal d’aquesta tesi doctoral és la síntesis i la caracterització d’espècies organometàl•liques i estables aril-Co(III), fent ús de salts de cobalt(II) i d’un lligand macrocíclic. Concretament, es focalitza l’atenció en el pas d’activació de l’enllaç
C-H per tal d’esbrinar quin és el mecanisme que opera en la activació d’enllaços
C-H catalitzada per espècies de cobalt en alt estat d’oxidació. Tanmateix, també es porta a terme l’estudi de la reactivitat de les especies organometàl•liques aril-Co(III) amb diferent parelles d’acoblament. D’una banda, s’estudia la formació d’anells fent ús d’alquins. D‘altra banda, s’estudia la inserció d’espècies metall-carbenoid en enllaços
C-H catalitzada per cobalt, fent ús d’etil diazo acetat. Finalment, aquesta reactivitat s’extrapola a substrats que contenen el grup 8-aminoquinolina. Així doncs, es desenvolupen metodologies per la síntesis de sulfonamides cícliques així com per la formació de 5- i 7-nitro-8-aminoquinolines fent ús d’alquins i nitrit de tert-butil, respectivament
Advisors/Committee Members: [email protected] (authoremail), false (authoremailshow), Ribas Salamaña, Xavi (director), Company Casadevall, Anna (director), true (authorsendemail).
Subjects/Keywords: Cobalt; Cobalto; C-H functionalization; C-H activation; Activació d'enllaços C-H; Activación de enlaces C-H; Catalysis; Catàlisi; Catálisis; 546
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APA (6th Edition):
Planas Fàbrega, O. (2018). Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies. (Thesis). Universitat de Girona. Retrieved from http://hdl.handle.net/10803/482111
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Planas Fàbrega, Oriol. “Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies.” 2018. Thesis, Universitat de Girona. Accessed December 08, 2019.
http://hdl.handle.net/10803/482111.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Planas Fàbrega, Oriol. “Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies.” 2018. Web. 08 Dec 2019.
Vancouver:
Planas Fàbrega O. Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies. [Internet] [Thesis]. Universitat de Girona; 2018. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/10803/482111.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Planas Fàbrega O. Cobalt-catalyzed C-H functionalization: from mechanistic studies to synthetic methodologies. [Thesis]. Universitat de Girona; 2018. Available from: http://hdl.handle.net/10803/482111
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
27.
Guilbaud, Johan.
Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes.
Degree: Docteur es, Chimie, 2018, Bourgogne Franche-Comté
URL: http://www.theses.fr/2018UBFCK047
► L’activation C–H d’aryle dirigée par des groupements directeurs 2-sulfonylpyridine et 2-sulfanylpyridine vers la formation de liaisons C–X (X = F, Cl, Br, I) a été…
(more)
▼ L’activation C–H d’aryle dirigée par des groupements directeurs 2-sulfonylpyridine et 2-sulfanylpyridine vers la formation de liaisons C–X (X = F, Cl, Br, I) a été étudiée. Pour cette étude, il a été nécessaire au préalable de développer des méthodes de synthèse de thioéthers (2-(arylsulfanyl)pyridines) et de sulfones (2 (arylsulfonyl)pyridines) simples et variées. La synthèse des thioéthers s’est effectuée à l’aide d’un couplage C–S catalysé au palladium entre des thioaryles et des hétérocycles halogénés. Ce couplage a pour avantage d’utiliser un ligand commercial et peu onéreux : la bis(diphénylphosphino)ferrocène (dppf). L’oxydation des thioéthers a ensuite été étudiée pour former des sulfones dans des conditions les plus performantes possibles. Enfin, l’halogénation de ces différents composés a pu être étudiée par activation de liaison C–H d’aryle ortho-dirigée en présence de complexes de palladium. Différents systèmes catalytiques ont été mis au point permettant la formation de liaisons C–Br, C–I, C–Cl et même C–F. Ces couplages ont l’avantage d’être sélectifs en positions ortho du groupement directeur et de pouvoir fonctionnaliser une seule ou les deux positions.
C–H activation of aryl compounds directed by 2-sulfonylpyridine and 2-sulfanylpyridine moiety for the formation of C–X (X = F, Cl, Br, I) bonds was studied. First, the syntheses of thioethers (2-(arylsulfanyl)pyridines) and sulfones (2-(arylsulfonyl)pyridines) were necessary for the progress of this project. A C–S coupling catalyzed by palladium complexe between thioaryls and halogenated heterocycles was performed for the synthesis of thioethers. The cheap ligand bis(diphenylphosphino)ferrocene (dppf) was used for this convenient reaction. Then, oxidation of thioethers was performed to synthesize sulfones. Halogenation of these compounds was studied with ortho-directed C–H activation catalyzed with palladium. Different catalytic systems were elaborated allowing the formations of C–Br, C–I, C–Cl and C–F bonds. These couplings are selective in ortho position of directing group and one or both positions can be functionalized.
Advisors/Committee Members: Hierso, Jean-Cyrille (thesis director), Roger, Julien (thesis director).
Subjects/Keywords: Oxydation; Couplage C–S; Activation C–H; Couplage C–halogène; Oxydation; Oxidation; C–H activation; Oxidation; C–halogen coupling; Palladium; 540; 541.39
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APA (6th Edition):
Guilbaud, J. (2018). Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes. (Doctoral Dissertation). Bourgogne Franche-Comté. Retrieved from http://www.theses.fr/2018UBFCK047
Chicago Manual of Style (16th Edition):
Guilbaud, Johan. “Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes.” 2018. Doctoral Dissertation, Bourgogne Franche-Comté. Accessed December 08, 2019.
http://www.theses.fr/2018UBFCK047.
MLA Handbook (7th Edition):
Guilbaud, Johan. “Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes.” 2018. Web. 08 Dec 2019.
Vancouver:
Guilbaud J. Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes. [Internet] [Doctoral dissertation]. Bourgogne Franche-Comté; 2018. [cited 2019 Dec 08].
Available from: http://www.theses.fr/2018UBFCK047.
Council of Science Editors:
Guilbaud J. Synthèses d'(arylsulfanyl)pyridines halogénées et leurs dérivés par couplages C-S et C-X catalysés par des complexes du palladium : Halogenated (arylsulfanyl)pyridines syntheses and their derivatives by C-S and C-X couplings catalyzed by palladium complexes. [Doctoral Dissertation]. Bourgogne Franche-Comté; 2018. Available from: http://www.theses.fr/2018UBFCK047
Texas A&M University
28.
Zhu, Yanjun.
Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis.
Degree: 2012, Texas A&M University
URL: http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965
► Strong bond activation mediated by pincer ligated transiton-metal complexes has been the subject of intense study in recent years, due to its potential involvement in…
(more)
▼ Strong bond
activation mediated by pincer ligated transiton-metal complexes has been the
subject of intense study in recent years, due to its potential involvement in catalytic transformations. This dissertation has focused on the net heterolytic cleavage of B-H and B-B bonds across the N-Pd bond in a cationic (PNP)Pd fragment, the
C-H oxidative addition to a (PNP)Ir center and the recent results on the
C-H and
C-O oxidative addition in reactions of aryl carboxylates with the (PNP)Rh fragment.
Transition metal carbene and carbyne complexes are of great interest because of their role in a wide variety of catalytic reactions. Our work has resulted in the isolation of a rhodium(I) difluorocarbene. Reaction of the rhodium difluorocarbene complex with a silylium salt led to the
C-F bond cleavage and the formation of a terminal fluorocarbyne complex.
Reductive elimination is a critical step of cross coupling reactions. In order to examine the effect of the pincer ligand on the reductive elimination reactions from Rh(III), the first pi-accepting PNP ligand bearing pyrrolyl substituents was prepared and installed onto the rhodium center. Arylhalide (halide = Br, I) oxidative addition was achieved in the presence of donor ligands such as acetonitrile to form stable six-coordinate Rh(III) compounds. The
C-O reductive elimination reactions in this system were also explored.
Advisors/Committee Members: Ozerov, Oleg V. (advisor), Gabba?, Fran?ois P. (committee member), Gladysz, John A. (committee member), Lane, Robert (committee member).
Subjects/Keywords: bond activation; transition-metal complxes; C-H activation; C-O activation; oxidative addition; reductive elimination; fluorocarbyne complex
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APA ·
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MLA ·
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CSE |
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APA (6th Edition):
Zhu, Y. (2012). Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis. (Thesis). Texas A&M University. Retrieved from http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Chicago Manual of Style (16th Edition):
Zhu, Yanjun. “Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis.” 2012. Thesis, Texas A&M University. Accessed December 08, 2019.
http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Zhu, Yanjun. “Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis.” 2012. Web. 08 Dec 2019.
Vancouver:
Zhu Y. Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis. [Internet] [Thesis]. Texas A&M University; 2012. [cited 2019 Dec 08].
Available from: http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Zhu Y. Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis. [Thesis]. Texas A&M University; 2012. Available from: http://hdl.handle.net/1969.1/ETD-TAMU-2012-05-10965
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
29.
Sofack-Kreutzer, Julien.
Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings.
Degree: Docteur es, Chimie organique, 2011, Université Claude Bernard – Lyon I
URL: http://www.theses.fr/2011LYO10302
► La fonctionnalisation de liaisons C-H réputées peu réactives ouvre de nouvelles perspectives en synthèse organique. La catalyse par un métal de transition comme le palladium…
(more)
▼ La fonctionnalisation de liaisons C-H réputées peu réactives ouvre de nouvelles perspectives en synthèse organique. La catalyse par un métal de transition comme le palladium représente une solution particulièrement efficace à ce problème. Les travaux de thèse présentés dans ce mémoire s’inscrivent dans ce contexte. Dans un premier temps, la réaction étudiée, catalysée par le palladium, a visé à étendre une méthodologie mise au point au laboratoire pour la synthèse de carbocycles et d’hétérocycles à cinq chaînons par activation intramoléculaire de liaisons C(sp3)-H à partir de chlorures d’aryles. Ces derniers sont en effet plus disponibles et moins onéreux que les bromures d’aryle correspondants. Des études d’optimisation ont été effectuées pour la mise au point d'une réaction diastéréosélective et régiosélective. Plusieurs substrats ont été synthétisés pour être ensuite placés dans les conditions optimales de la réaction d’activation C(sp3)-H, et ont conduit à une grande diversité de cycles à cinq chaînons fusionnés. Dans un deuxième temps, nos travaux ont consisté à étendre l’activation C(sp3)-H pallado-catalysée à des précurseurs non aromatiques cycliques ou acycliques. Pour des raisons d'accessibilité, nos études se sont alors portées sur la préparation de bromures vinyliques azotés pouvant conduire après activation C-H à des motifs hexahydroindoles ou pyrrolidines. De nouvelles conditions d’activation CH ont alors été trouvées pour cette famille de substrats, et ont conduit aux hétérocycles cibles de manière diastéréosélective et régiosélective. Après extension de la réaction à divers précurseurs, nous nous sommes intéressés à la synthèse d’un intermédiaire poly-fonctionnalisé permettant d'accéder aux aéruginosines, famille de produits naturels bioactifs.
The direct functionalization of unactivated C-H bonds represents an atom- and step-economical alternative to more traditional synthetic methods based on functional group transformation, which often require multi-step sequences. In particular, transition-metal catalysis has recently emerged as a owerful tool to functionalize otherwise unreactive C-H bonds. In this context, we first investigated the extension of a methodology that has been developed in our laboratory for the synthesis of fused five-membered rings via palladium-catalyzed C(sp3)-H activation from aryl chlorides. Optimization studies were conducted and reaction conditions leading to a regioand diastereoselective process were found. These optimal conditions were applied to various ubstrates, giving rise to a variety of fused five-membered carbocycles and heterocycles. Next, our work was devoted to the extension of the palladium-catalyzed C(sp3)-H activation to cyclic and acyclic non aromatic precursors. Our studies focused on the preparation of the more accessible nitrogen-containing bromoalkene substrates, leading to interesting hexahydroindole or pyrrolidine motifs by C-H activation. New C-H activation conditions were adapted to this family of substrates and led to the synthesis of the target…
Advisors/Committee Members: Baudoin, Olivier (thesis director).
Subjects/Keywords: Fonctionnalisation C-H; Activation C-H; Indanes; Indolines; Catalyse organométallique; Chloroarènes; Formation de liaisons C-C; Palladium; Bromoalcènes; Hexahydroindoles; Aéruginosines; C-H functionalization; C-H activation; Indanes; Indoles; Organometallic catalysis; C-C bond formation; Palladium; Hexahydroindoles; Aeruginosins; 547
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APA ·
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MLA ·
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APA (6th Edition):
Sofack-Kreutzer, J. (2011). Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings. (Doctoral Dissertation). Université Claude Bernard – Lyon I. Retrieved from http://www.theses.fr/2011LYO10302
Chicago Manual of Style (16th Edition):
Sofack-Kreutzer, Julien. “Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings.” 2011. Doctoral Dissertation, Université Claude Bernard – Lyon I. Accessed December 08, 2019.
http://www.theses.fr/2011LYO10302.
MLA Handbook (7th Edition):
Sofack-Kreutzer, Julien. “Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings.” 2011. Web. 08 Dec 2019.
Vancouver:
Sofack-Kreutzer J. Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings. [Internet] [Doctoral dissertation]. Université Claude Bernard – Lyon I; 2011. [cited 2019 Dec 08].
Available from: http://www.theses.fr/2011LYO10302.
Council of Science Editors:
Sofack-Kreutzer J. Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées : Intramolecular Palladium-Catalyzed C(sp3)-H Arylation of aryl and alkenyl halides : synthesis of fused five-membered rings. [Doctoral Dissertation]. Université Claude Bernard – Lyon I; 2011. Available from: http://www.theses.fr/2011LYO10302
Clemson University
30.
Zhang, Jack.
Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst.
Degree: PhD, Chemical Engineering, 2011, Clemson University
URL: https://tigerprints.clemson.edu/all_dissertations/753
► Proton exchange membrane fuel cells are a highly efficient source of power generation that is needed to sustain the energy demands of today's more environmentally…
(more)
▼ Proton exchange membrane fuel cells are a highly efficient source of power generation that is needed to sustain the energy demands of today's more environmentally conscience society. However, the presence of impurities in the hydrogen fuel stream, such as CO, H
2S, and NH
3 from the steam reforming/partial oxidation of hydrocarbons/methanol, can severely poison the Pt electrocatalyst present in the fuel cell electrode causing degradation in the fuel cell performance. To counter these poisoning effects, fuel cell manufacturers are forced to use higher Pt loadings, which dramatically increases material costs and prevents the successful commercialization of the technology. The focus of the present research is the investigation of the impurity effects on the activity of a Pt fuel cell catalyst for the adsorption and
activation of hydrogen at typical fuel cell conditions. The degree of impact from each impurity is observed in terms of Pt surface atom availability, which is then related to fuel cell performance results. The effect of CO on hydrogen
activation on Pt fuel cell catalysts were found to be severe even at as low as 10 ppm. In the presence of water vapor, the maximum CO surface coverage found on the Pt/
C catalyst was between 0.5–0.7 monolayer at typical fuel cell operating conditions. Reversibility of the poisoning showed only a partial recovery in available Pt surface sites, however, the amount of Pt surface sites recovered was enough to return the hydrogen
activation reaction back to equilibrium, which is equivalent to a full recovery observed in fuel cell performance. The poisoning effect from tetrachloroethylene appears to be a combination of the processes occurring at the anode and cathode. The presence of the hydrogen is required to help decompose the chlorocarbon at the low operating temperatures. Once decomposed, the oxygen enhances the poisoning by tetrachloroethylene or derivatives. Other impurities such as NH
3, paraffins (
C3–
C7), inert gases (He, N
2, Ar), and ethylene, were found to have little or no effect on the hydrogen
activation on Pt fuel cell catalyst.
Advisors/Committee Members: Goodwin, Jr., James G, Bruce , David A, Hwu , Shiou-Jyh, Kitchens , Christopher L.
Subjects/Keywords: Fuel Cell Poisoning; Hydrogen Activation; Impurity Effects; Nafion-Pt/C; PEMFC; Pt/C; Chemical Engineering
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APA ·
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APA (6th Edition):
Zhang, J. (2011). Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst. (Doctoral Dissertation). Clemson University. Retrieved from https://tigerprints.clemson.edu/all_dissertations/753
Chicago Manual of Style (16th Edition):
Zhang, Jack. “Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst.” 2011. Doctoral Dissertation, Clemson University. Accessed December 08, 2019.
https://tigerprints.clemson.edu/all_dissertations/753.
MLA Handbook (7th Edition):
Zhang, Jack. “Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst.” 2011. Web. 08 Dec 2019.
Vancouver:
Zhang J. Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst. [Internet] [Doctoral dissertation]. Clemson University; 2011. [cited 2019 Dec 08].
Available from: https://tigerprints.clemson.edu/all_dissertations/753.
Council of Science Editors:
Zhang J. Effects on Hydrogen Adsorption and Activation on Platinum in a Fuel Cell Catalyst. [Doctoral Dissertation]. Clemson University; 2011. Available from: https://tigerprints.clemson.edu/all_dissertations/753
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Open Access Theses and Dissertations