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Dalhousie University
1.
Lavery, Christopher B.
THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.
Degree: PhD, Department of Chemistry, 2013, Dalhousie University
URL: http://hdl.handle.net/10222/37533 
► In the pursuit of increasingly efficient and/or new chemical transformations, homogeneous transition metal catalysts are proving to be invaluable components of the synthetic chemist’s toolbox.…
(more)
▼ In the pursuit of increasingly efficient and/or new
chemical transformations, homogeneous transition metal catalysts
are proving to be invaluable components of the synthetic chemist’s
toolbox. Notwithstanding the many important contributions made to
the area of synthetic chemistry utilizing other transition metal
catalysts,
palladium-catalyzed cross-coupling techniques have been
demonstrated to allow for a plethora of otherwise very difficult or
even impossible bond forming reactions to be realized. In this
context, appropriately designed ancillary ligands, which upon
binding to a metal center can influence metal-centred reactivity,
have played an essential role in the advancement of
palladium-catalyzed cross-coupling reactions. This thesis describes
a multi-faceted approach to the identification of effective ligands
for the
palladium-catalyzed construction of (sp2)carbon-nitrogen
and -oxygen bonds. A new series of P,O-DalPhos ligands were
developed and applied in the synthesis of of N-substituted indoles
via tandem
palladium-catalyzed cross-coupling/cyclizations of
ortho-alkynylhalo(hetero)arenes with primary amines. Notably, one
P,O-DalPhos variant, OTips-DalPhos, was demonstrated to offer the
broadest known substrate scope in this important class of
transformations, affording a variety of structurally diverse
indoles and related heterocyclic derivatives in high yields. Also
described herein is the identification of the previously reported
ligand BippyPhos as an extremely robust and versatile ligand in
both
palladium-catalyzed carbon-nitrogen and -oxygen cross-coupling
applications. Indeed, the use of a Pd/BippyPhos catalyst enabled
the cross-coupling of a range of (hetero)aryl (pseudo)halides with
primary and secondary amines, NH heterocycles, amides, ammonia and
hydrazine, with representative examples being accommodated in air.
The unprecedented scope of the Pd/BippyPhos catalyst in
carbon-nitrogen cross-coupling allowed for the development of two
novel one-pot, two-step syntheses of N¬-aryl heterocycles from
ammonia, ortho-alkynylhalo(hetero)arenes and (hetero)aryl halides
through tandem N-arylation/hydroamination reactions. A marked
selectivity profile was also observed for the Pd/BippyPhos catalyst
and successfully exploited in the chemoselective monoarylation of
substrates featuring two distinct and potentially reactive
NH-containing moieties. Finally, Pd/BippyPhos mixtures served as
robust and efficient catalysts for the hydroxylation of a range of
(hetero)aryl halides and ortho-alkynyl(halo)heteroarenes to form
phenols and phenol-derived heterocycles.
Advisors/Committee Members: Dr. Bruce Arndtsen (external-examiner), Dr. Mark Stradiotto (graduate-coordinator), Dr. Laura Turculet, Dr. Kevin Grundy and Dr. Alison Thompson (thesis-reader), Dr. Mark Stradiotto (thesis-supervisor), Not Applicable (ethics-approval), Not Applicable (manuscripts), Not Applicable (copyright-release).
Subjects/Keywords: Palladium; Catalysis; Ligands
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APA (6th Edition):
Lavery, C. B. (2013). THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. (Doctoral Dissertation). Dalhousie University. Retrieved from http://hdl.handle.net/10222/37533
Chicago Manual of Style (16th Edition):
Lavery, Christopher B. “THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.” 2013. Doctoral Dissertation, Dalhousie University. Accessed March 04, 2021.
http://hdl.handle.net/10222/37533.
MLA Handbook (7th Edition):
Lavery, Christopher B. “THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.” 2013. Web. 04 Mar 2021.
Vancouver:
Lavery CB. THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. [Internet] [Doctoral dissertation]. Dalhousie University; 2013. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/10222/37533.
Council of Science Editors:
Lavery CB. THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS
IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. [Doctoral Dissertation]. Dalhousie University; 2013. Available from: http://hdl.handle.net/10222/37533
Montana State University
2.
Aebly, Andrew Henry.
The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.
Degree: PhD, College of Letters & Science, 2015, Montana State University
URL: https://scholarworks.montana.edu/xmlui/handle/1/10151
► Palladium catalysis has been utilized extensively in organic chemistry for the synthesis of complex molecules. Despite its abundant use and many successful applications, there remain…
(more)
▼ Palladium catalysis has been utilized extensively in organic chemistry for the synthesis of complex molecules. Despite its abundant use and many successful applications, there remain challenging transformations, specifically with developing new chiral centers. The aim of this research was to explore the underdeveloped, weakly coordinating X-type ligands and their applicability in enantioselective reactions. The electrophilic catalyst, generated by the coordination of sulfonic or phosphoric acid ligands, was utilized to explore underfunctionalized starting materials, such as unactivated alkenes and aryl C-H bonds. Herein we report two Pd II-catalyzed enantioselective transformations: oxidative amination and 1,2-carboamination. The Wacker-type oxidative amination was accomplished with good yields and modest enantioselectivity in the synthesis of chiral indolines and a cyclic carbamate. Substantial loss in enantioselectivity was seen with ortho-substituted anilines. The 1,2-carboamination coupled a mild, directing group facilitated C-H activation on a series of aryl ureas with a subsequent chiral C-N bond formation. Electron-rich, para-substituted aryl ureas provided the highest consistent yields and enantioselectivities. Electron deficient substrates provided little reactivity and substitutions at the ortho- and meta-positions gave inconsistent results. To our knowledge these transformations mark the first enantioselective examples of Pd II-catalyzed oxidative transformations utilizing chiral sulfonic acid ligands.
Advisors/Committee Members: Chairperson, Graduate Committee: Trevor J. Rainey (advisor).
Subjects/Keywords: Palladium.; Catalysis.; Ligands.
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APA (6th Edition):
Aebly, A. H. (2015). The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. (Doctoral Dissertation). Montana State University. Retrieved from https://scholarworks.montana.edu/xmlui/handle/1/10151
Chicago Manual of Style (16th Edition):
Aebly, Andrew Henry. “The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.” 2015. Doctoral Dissertation, Montana State University. Accessed March 04, 2021.
https://scholarworks.montana.edu/xmlui/handle/1/10151.
MLA Handbook (7th Edition):
Aebly, Andrew Henry. “The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.” 2015. Web. 04 Mar 2021.
Vancouver:
Aebly AH. The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. [Internet] [Doctoral dissertation]. Montana State University; 2015. [cited 2021 Mar 04].
Available from: https://scholarworks.montana.edu/xmlui/handle/1/10151.
Council of Science Editors:
Aebly AH. The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. [Doctoral Dissertation]. Montana State University; 2015. Available from: https://scholarworks.montana.edu/xmlui/handle/1/10151
University of Michigan
3.
Peterson, Luke.
New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism.
Degree: PhD, Chemistry, 2017, University of Michigan
URL: http://hdl.handle.net/2027.42/138673
► Biologically active compounds, such as molecules isolated from natural sources like plants and marine sponges, have long been of interest to the synthetic chemistry community.…
(more)
▼ Biologically active compounds, such as molecules isolated from natural sources like plants and marine sponges, have long been of interest to the synthetic chemistry community. Synthetic routes towards these biologically interesting compounds are constantly being sought after and improved upon by synthetic chemists, because efficient synthetic routes yield not only the compound in question in mass quantitites, but also allow for the formation of a library of compounds bearing small changes in structure that are not found in the originally isolated compound. These small changes can potentially have dramatic effects on the biological activity of the compounds in question.
Nitrogen containing heterocycles appear in a wide variety of these aforementioned biologically active compounds, and for this reason have long been an attractive target to the synthetic community. Heterocyclic scaffolds such as substituted pyrrolidines are present in compounds that display a wide variety of biological activity, such as antifungal, antibiotic, and antitumor properties. Cyclic guanidines are also present in a large number of biologically interesting molecules, such as compounds that display antibiotic, immunosuppressive, and neurotoxic properties. While synthetic methodologies to access the scaffolds in question currently exist, the majority of them rely on preexisting substitution present in the substrate to afford the desired substituted products. This precludes the ability to rapidly synthesize a library of compounds with various substitution patterns that can then be assayed for changes in biological activity.
The research described in this dissertation details the development of a methodology to synthesize substituted, nitrogen containing heterocycles in a
palladium catalyzed, modular coupling reaction. Chapter 1 outlines the biological relevance of nitrogen containing heterocycles, and it details the previous efforts of the Wolfe group to synthesize the molecular scaffolds in question. Chapter 2 describes the synthesis of substituted pyrrolidines via a newly developed, anti-aminopalladation methodology. Substituted pyrrolidine products bearing previously unusable N-tosyl and N-trifluoroacetyl protecting groups were afforded in good yield. Chapters 3 and 4 detail the synthesis of substituted, cyclic guanidines from acyclic N-allyl guanidine substrates. Chapter 3 focuses on coupling said guanidine substrates with aryl halides/triflates, in which substrates bearing cleavable N-cyano and N-tosyl protecting groups were utilized. Finally, Chapter 4 describes the successful coupling of guanidine substrates bearing N-cyano and N-tosyl protectin groups with OBz-protected amine electrophiles in a variation on a 1,2-diamination reaction.
Advisors/Committee Members: Wolfe, John P (committee member), Soellner, Matthew Bryan (committee member), Montgomery, John (committee member), Sanford, Melanie S (committee member).
Subjects/Keywords: Palladium Catalysis; Chemistry; Science
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APA (6th Edition):
Peterson, L. (2017). New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism. (Doctoral Dissertation). University of Michigan. Retrieved from http://hdl.handle.net/2027.42/138673
Chicago Manual of Style (16th Edition):
Peterson, Luke. “New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism.” 2017. Doctoral Dissertation, University of Michigan. Accessed March 04, 2021.
http://hdl.handle.net/2027.42/138673.
MLA Handbook (7th Edition):
Peterson, Luke. “New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism.” 2017. Web. 04 Mar 2021.
Vancouver:
Peterson L. New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism. [Internet] [Doctoral dissertation]. University of Michigan; 2017. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/2027.42/138673.
Council of Science Editors:
Peterson L. New Developments in Heterocycle Synthesis: Applications of an Anti-Aminopalladation Mechanism. [Doctoral Dissertation]. University of Michigan; 2017. Available from: http://hdl.handle.net/2027.42/138673
University of Bristol
4.
Glaisyer, Beth.
The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.
Degree: PhD, 2020, University of Bristol
URL: http://hdl.handle.net/1983/fb29e716-9b23-4965-b181-c41feb18a24b
► A novel Pd(II)-catalysed C–H activation/aza-Wacker cascade sequence has been optimised for indoles bearing an N-tethered alkene and an N-acyl mesylamide group that serves dual purpose…
(more)
▼ A novel Pd(II)-catalysed C–H activation/aza-Wacker cascade sequence has been optimised for indoles bearing an N-tethered alkene and an N-acyl mesylamide group that serves dual purpose as a directing group and a C–N bond precursor. This optimisation was achieved by a combination of Design of Experiments and traditional reactant screening. The reaction is tolerant to functionalisation on the alkene and tether, as well as substitution at various positions around the indole ring. The methodology can also be applied to pyrrole systems. 24 successful examples of this Pd(II)-catalysed C–H activation methodology are described. A number of studies have been carried out in order to probe the mechanism of this cascade sequence. As a result of this an oxidative Heck/aza-Wacker mechanism beginning with amide deprotonation can be proposed. The application of this methodology to non-aromatic substrates, with a view to this being used as a potential key step towards the total synthesis of naturally occurring alkaloids and potential drug discovery scaffolds, was examined. The synthesis of the substrate necessary for the total synthesis of the alkaloid matrine was unsuccessful, so the Pd(II)-catalysed C–H activation of enamine test substrates were instead investigated. These substrates were found to be unsuitable for Pd(II)-catalysed C–H activation due to a lack of aromaticity and a lack of electron density. Proof of concept for the oxidative Heck/aza-Wacker cascade cyclisation of aniline-derived substrates is also described.
Subjects/Keywords: Palladium; C-H Activation; Catalysis
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APA ·
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APA (6th Edition):
Glaisyer, B. (2020). The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. (Doctoral Dissertation). University of Bristol. Retrieved from http://hdl.handle.net/1983/fb29e716-9b23-4965-b181-c41feb18a24b
Chicago Manual of Style (16th Edition):
Glaisyer, Beth. “The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.” 2020. Doctoral Dissertation, University of Bristol. Accessed March 04, 2021.
http://hdl.handle.net/1983/fb29e716-9b23-4965-b181-c41feb18a24b.
MLA Handbook (7th Edition):
Glaisyer, Beth. “The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.” 2020. Web. 04 Mar 2021.
Vancouver:
Glaisyer B. The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. [Internet] [Doctoral dissertation]. University of Bristol; 2020. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/1983/fb29e716-9b23-4965-b181-c41feb18a24b.
Council of Science Editors:
Glaisyer B. The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. [Doctoral Dissertation]. University of Bristol; 2020. Available from: http://hdl.handle.net/1983/fb29e716-9b23-4965-b181-c41feb18a24b
Penn State University
5.
Senftle, Thomas Patrick.
Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts.
Degree: 2015, Penn State University
URL: https://submit-etda.libraries.psu.edu/catalog/26182
► In Pd/ceria catalysts, mixed Pd-Ce oxide formations at the cluster-support interface offer unique activity toward hydrocarbon activation. Both experimental and computational investigations in the literature…
(more)
▼ In Pd/ceria catalysts, mixed Pd-Ce oxide formations at the cluster-support interface offer unique activity toward hydrocarbon activation. Both experimental and computational investigations in the literature suggest that unique Pd-O-Ce surface formations yield highly reactive sites on the catalyst surface. However, structural details and the corresponding reaction mechanisms governing the behavior of such sites are not well understood. As such, this dissertation employs Density Functional Theory (DFT) in tandem with classical ReaxFF modeling to determine the stability and activity of methane activation sites at the Pd/ceria interface.
The ReaxFF interaction potential is used to investigate cluster-support interactions at length and time scales inaccessible to quantum methods. In particular, this dissertation develops a hybrid grand canonical Monte Carlo/molecular dynamics (GC-MC/MD) approach that is suited to assess oxide formation in regions where the Pd cluster contacts the underlying ceria support. When coupled with DFT, this multi-scale approach demonstrates that Pd atoms incorporated in the fluorite lattice structure of ceria alternate between Pd4+ and Pd2+ oxidation states during operation. In general, Pd4+ states are effective hydrocarbon activation sites, as the dissociative adsorption of the hydrocarbon reduces Pd4+ to its thermodynamically preferred Pd2+ state. Therefore, maximizing the number of transient Pd4+ states under operating conditions is essential for achieving optimal catalytic performance. The multi-scale simulation methodology developed and applied in this dissertation can evaluate the trade-off between stability and activity exhibited by Pd/CeO2, and can be readily extended to other catalytic systems.
Advisors/Committee Members: Michael John Janik, Dissertation Advisor/Co-Advisor, Michael John Janik, Committee Chair/Co-Chair, Adrianus C Van Duin, Committee Chair/Co-Chair, Robert Martin Rioux Jr., Committee Member, Scott Thomas Milner, Committee Member.
Subjects/Keywords: Catalysis; DFT; ReaxFF; Palladium; Ceria
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APA (6th Edition):
Senftle, T. P. (2015). Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts. (Thesis). Penn State University. Retrieved from https://submit-etda.libraries.psu.edu/catalog/26182
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):
Senftle, Thomas Patrick. “Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts.” 2015. Thesis, Penn State University. Accessed March 04, 2021.
https://submit-etda.libraries.psu.edu/catalog/26182.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Senftle, Thomas Patrick. “Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts.” 2015. Web. 04 Mar 2021.
Vancouver:
Senftle TP. Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts. [Internet] [Thesis]. Penn State University; 2015. [cited 2021 Mar 04].
Available from: https://submit-etda.libraries.psu.edu/catalog/26182.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Senftle TP. Development of Multi-scale Computational Methods for Modeling Phase Formation in Pd-Based Catalysts. [Thesis]. Penn State University; 2015. Available from: https://submit-etda.libraries.psu.edu/catalog/26182
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of the Western Cape
6.
Van Wyk, Shane Cedrick.
Some new bimetallic nickel and palladium complexes for catalysis applications
.
Degree: 2015, University of the Western Cape
URL: http://hdl.handle.net/11394/4873
► This thesis reports on the syntheses of new bimetallic iminopyridyl nickel(II) and palladium(II) complexes as catalyst precursors for ethylene ligomerization/polymerization. Tetrahydrophenyl-linked iminopyridyl ligands, pyridin-2-ylmethyl-{4-[(pyridin-2-ylmethylimino)-methyl]-benzylidene}-amine (L1)…
(more)
▼ This thesis reports on the syntheses of new bimetallic iminopyridyl nickel(II) and
palladium(II) complexes as catalyst precursors for ethylene ligomerization/polymerization. Tetrahydrophenyl-linked iminopyridyl ligands, pyridin-2-ylmethyl-{4-[(pyridin-2-ylmethylimino)-methyl]-benzylidene}-amine (L1) and (2-pyridin-2-yl-ethyl)-{4-[(2-pyridin-2-yl-ethylimino)-methyl]-benzylidene}-amine (L2) were prepared via condensation from terephthaldehyde and 2 molar equivalents of a primary pyridylamine. Alkyl-linked iminopyridyl ligands N,N'-bis-pyridin-2-ylmethylene-propane-1,3-diamine (L3), N,N'-bispyridin-
2-ylmethylene-butane-1,4-diamine (L4) and N,N'-bis-pyridin-2-ylmethylenepentane-
1,5-diamine (L5) were prepared by condensation of 2 equivalents of 2-
pyridinecarboxaldehyde and a primary diamine. The ligands were obtained as either red oils or orange solids. These ligands were characterized using Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS), elemental analysis (EA), ultraviolet-visible spectrophotometry (UV-Vis) and thermal gravimetric analysis (TGA) where applicable. The tetrahydrophenyl-linked iminopyridyl ligands were subsequently used to prepare their corresponding homobimetallic
palladium(II) and nickel(II) complexes. A 1:2 reaction of the ligands with PdCl2(COD), NiCl2(DME) and NiBr2(DME) gave
palladium(II) and nickel(II) complexes C1-C6 in moderate to very good yields (58-94%). The
palladium(II) complexes were found to be stable, but light-sensitive solids while the nickel(II) complexes were found to be stable, but light and air sensitive solids. These complexes were characterized using FTIR, NMR, EA, MS, UV-Vis and TGA. These complexes were then tested for catalytic activity of ethylene oligomerization. It was found that complexes C1 and C5 were highly active when activated by the cocatalysts methylaluminoxane (MAO) as well as ethyl aluminium dichloride (EADC). It was found that EADC gave the highest activity so the remaining catalysts (C3 and C6) were tested exclusively with EADC. All four complexes were active for ethylene oligomerization with yields of between 2.7-6.5 g, with C5 providing the highest activity and C1 the lowest. These catalysts were highly selective towards C4 oligomers with percentages ranging from 71-81%.
Optimization studies were then carried out with C3 by varying the pressure and Al:Ni ratio.
Advisors/Committee Members: Onani, Martin (advisor).
Subjects/Keywords: Iminopyridyl ligands;
Catalysis;
Nickel;
Palladium
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APA ·
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APA (6th Edition):
Van Wyk, S. C. (2015). Some new bimetallic nickel and palladium complexes for catalysis applications
. (Thesis). University of the Western Cape. Retrieved from http://hdl.handle.net/11394/4873
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):
Van Wyk, Shane Cedrick. “Some new bimetallic nickel and palladium complexes for catalysis applications
.” 2015. Thesis, University of the Western Cape. Accessed March 04, 2021.
http://hdl.handle.net/11394/4873.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Van Wyk, Shane Cedrick. “Some new bimetallic nickel and palladium complexes for catalysis applications
.” 2015. Web. 04 Mar 2021.
Vancouver:
Van Wyk SC. Some new bimetallic nickel and palladium complexes for catalysis applications
. [Internet] [Thesis]. University of the Western Cape; 2015. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/11394/4873.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Van Wyk SC. Some new bimetallic nickel and palladium complexes for catalysis applications
. [Thesis]. University of the Western Cape; 2015. Available from: http://hdl.handle.net/11394/4873
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Minnesota
7.
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 March 04, 2021.
http://hdl.handle.net/11299/165789.
MLA Handbook (7th Edition):
Rondla, Naveen Reddy. “Development of new reaction methodologies using palladium catalysts.” 2014. Web. 04 Mar 2021.
Vancouver:
Rondla NR. Development of new reaction methodologies using palladium catalysts. [Internet] [Doctoral dissertation]. University of Minnesota; 2014. [cited 2021 Mar 04].
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 Bristol
8.
Glaisyer, Beth.
The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.
Degree: PhD, 2020, University of Bristol
URL: https://research-information.bris.ac.uk/en/studentTheses/fb29e716-9b23-4965-b181-c41feb18a24b
;
https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.801607
► A novel Pd(II)-catalysed C–H activation/aza-Wacker cascade sequence has been optimised for indoles bearing an N-tethered alkene and an N-acyl mesylamide group that serves dual purpose…
(more)
▼ A novel Pd(II)-catalysed C–H activation/aza-Wacker cascade sequence has been optimised for indoles bearing an N-tethered alkene and an N-acyl mesylamide group that serves dual purpose as a directing group and a C–N bond precursor. This optimisation was achieved by a combination of Design of Experiments and traditional reactant screening. The reaction is tolerant to functionalisation on the alkene and tether, as well as substitution at various positions around the indole ring. The methodology can also be applied to pyrrole systems. 24 successful examples of this Pd(II)-catalysed C–H activation methodology are described. A number of studies have been carried out in order to probe the mechanism of this cascade sequence. As a result of this an oxidative Heck/aza-Wacker mechanism beginning with amide deprotonation can be proposed. The application of this methodology to non-aromatic substrates, with a view to this being used as a potential key step towards the total synthesis of naturally occurring alkaloids and potential drug discovery scaffolds, was examined. The synthesis of the substrate necessary for the total synthesis of the alkaloid matrine was unsuccessful, so the Pd(II)-catalysed C–H activation of enamine test substrates were instead investigated. These substrates were found to be unsuitable for Pd(II)-catalysed C–H activation due to a lack of aromaticity and a lack of electron density. Proof of concept for the oxidative Heck/aza-Wacker cascade cyclisation of aniline-derived substrates is also described.
Subjects/Keywords: Palladium; C-H Activation; Catalysis
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APA (6th Edition):
Glaisyer, B. (2020). The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. (Doctoral Dissertation). University of Bristol. Retrieved from https://research-information.bris.ac.uk/en/studentTheses/fb29e716-9b23-4965-b181-c41feb18a24b ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.801607
Chicago Manual of Style (16th Edition):
Glaisyer, Beth. “The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.” 2020. Doctoral Dissertation, University of Bristol. Accessed March 04, 2021.
https://research-information.bris.ac.uk/en/studentTheses/fb29e716-9b23-4965-b181-c41feb18a24b ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.801607.
MLA Handbook (7th Edition):
Glaisyer, Beth. “The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles.” 2020. Web. 04 Mar 2021.
Vancouver:
Glaisyer B. The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. [Internet] [Doctoral dissertation]. University of Bristol; 2020. [cited 2021 Mar 04].
Available from: https://research-information.bris.ac.uk/en/studentTheses/fb29e716-9b23-4965-b181-c41feb18a24b ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.801607.
Council of Science Editors:
Glaisyer B. The development of Pd(II)-catalysed C-H activation cascades for the synthesis of polyheterocycles. [Doctoral Dissertation]. University of Bristol; 2020. Available from: https://research-information.bris.ac.uk/en/studentTheses/fb29e716-9b23-4965-b181-c41feb18a24b ; https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.801607
University of Cambridge
9.
Whitehurst, William.
Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates.
Degree: PhD, 2020, University of Cambridge
URL: https://www.repository.cam.ac.uk/handle/1810/309480
► The search for new and distinct disconnection strategies is one of the foremost challenges in synthetic organic chemistry. To this end, transition metal-catalyzed C–H functionalization…
(more)
▼ The search for new and distinct disconnection strategies is one of the foremost challenges in synthetic organic chemistry. To this end, transition metal-catalyzed C–H functionalization represents a current area of research which aims to develop transformations that directly convert C–H bonds to C–C or C–heteroatom bonds, often enabling the synthesis of functionalized products that are not readily accessible using classical synthetic methods. The work disclosed in this thesis concerns the Pd-mediated C–H functionalization of unprotected aliphatic amines, in which the amine nitrogen coordinates to the Pd centre to promote cyclometalation to the key palladacycle intermediate. Specifically, research focused on the design and optimization of novel oxidants that would provide mild and general conditions to oxidize amine-derived palladacycles to high valent PdIV intermediates capable of undergoing a variety of reductive elimination pathways to afford a diverse range of functionalized products. Hypervalent iodine(III) reagents were initially investigated as oxidants in the development of a Pd-catalyzed intramolecular γ C–H amination process to form azetidine products from hindered cyclic amines. Following this, aryl halides containing coordinating groups at the ortho position were discovered as efficient palladacycle oxidants in which the ortho-group pre-coordinates to the palladium centre to facilitate the oxidative addition of the carbon–halogen bond. Employing 2-halobenzoic acid reagents, a Pd-catalyzed γ C–H arylation of acyclic secondary amines was developed involving in situ decarboxylation of the aryl group. Conversely, exchanging the ortho-carboxylic group for an acyl sulfonamide resulted in a switch in the selectivity of reductive elimination to form azetidines. Subsequently, organometallic studies using an aryl iodide reagent containing two ortho-carboxylic acid groups provided access to isolable aminoalkyl Pd(IV) complexes that were stable at room temperature, allowing for the study of the structure and reactivity of these previously elusive high valent intermediates. In addition to C(sp3)–H functionalization of all-alkyl amines, C(sp2)–H functionalization of benzylamines was investigated, with a modified aryl iodide reagent enabling a Pd-catalyzed C–H arylation-lactamization process to form a 7-membered ring lactam product. Finally, a stoichiometric study on benzylamine-derived palladacycles led to the discovery of an unprecedented dehydrogenative intramolecular C–C coupling reaction under oxidative conditions employing 2,6-pyridinedicarboxylic acid and an electrophilic fluorine oxidant. Preliminary investigations provided support for a Pd(IV)-mediated C–H activation step preceding C–C bond formation.
Subjects/Keywords: Palladium; Catalysis; Amines; Synthesis
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APA ·
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MLA ·
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APA (6th Edition):
Whitehurst, W. (2020). Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates. (Doctoral Dissertation). University of Cambridge. Retrieved from https://www.repository.cam.ac.uk/handle/1810/309480
Chicago Manual of Style (16th Edition):
Whitehurst, William. “Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates.” 2020. Doctoral Dissertation, University of Cambridge. Accessed March 04, 2021.
https://www.repository.cam.ac.uk/handle/1810/309480.
MLA Handbook (7th Edition):
Whitehurst, William. “Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates.” 2020. Web. 04 Mar 2021.
Vancouver:
Whitehurst W. Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates. [Internet] [Doctoral dissertation]. University of Cambridge; 2020. [cited 2021 Mar 04].
Available from: https://www.repository.cam.ac.uk/handle/1810/309480.
Council of Science Editors:
Whitehurst W. Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates. [Doctoral Dissertation]. University of Cambridge; 2020. Available from: https://www.repository.cam.ac.uk/handle/1810/309480
University of Cambridge
10.
Buettner, Cornelia.
Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines.
Degree: PhD, 2020, University of Cambridge
URL: https://www.repository.cam.ac.uk/handle/1810/315124
► Synthetic transformations on medicinally-relevant aliphatic amines are valuable in the diversification of molecules designed as pharmaceutical agents. This thesis describes two Csp3–H functionalisation reactions, using…
(more)
▼ Synthetic transformations on medicinally-relevant aliphatic amines are valuable in the diversification of molecules designed as pharmaceutical agents. This thesis describes two Csp3–H functionalisation reactions, using native amines (secondary and tertiary) to direct C–H activation. Chapter 2 describes a palladium-catalysed Csp3–H acetoxylation directed by native secondary amines. A range of cyclic amines could be acetoxylated with excellent functional group tolerance to form the desired functionalised products. Kinetic experiments and DFT calculations elucidated the mechanism of the transformation, which features C–O bond formation via an external acetate attack onto the electrophilic C–Pd bond. Chapter 3 describes a palladium-catalysed Csp3–H alkenylation directed by tertiary aliphatic amines. A diverse set of amines were functionalised using alkenyl boronic ester coupling partners to give the desired olefinated products. The work includes enantioselective functionalisation using a chiral ligand and a preliminary study of stoichiometric aminoalkyl palladium(II) complexes.
Subjects/Keywords: C-H Activation; Palladium catalysis
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APA ·
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APA (6th Edition):
Buettner, C. (2020). Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines. (Doctoral Dissertation). University of Cambridge. Retrieved from https://www.repository.cam.ac.uk/handle/1810/315124
Chicago Manual of Style (16th Edition):
Buettner, Cornelia. “Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines.” 2020. Doctoral Dissertation, University of Cambridge. Accessed March 04, 2021.
https://www.repository.cam.ac.uk/handle/1810/315124.
MLA Handbook (7th Edition):
Buettner, Cornelia. “Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines.” 2020. Web. 04 Mar 2021.
Vancouver:
Buettner C. Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines. [Internet] [Doctoral dissertation]. University of Cambridge; 2020. [cited 2021 Mar 04].
Available from: https://www.repository.cam.ac.uk/handle/1810/315124.
Council of Science Editors:
Buettner C. Palladium-Catalysed Functionalisation of Csp3–H Bonds Directed by Aliphatic Amines. [Doctoral Dissertation]. University of Cambridge; 2020. Available from: https://www.repository.cam.ac.uk/handle/1810/315124
Université Catholique de Louvain
11.
Nahra, Fady.
Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions.
Degree: 2013, Université Catholique de Louvain
URL: http://hdl.handle.net/2078.1/133426
► In this thesis we are going to first discuss the application of a copper hydride system, which was previously developed in our lab, to new…
(more)
▼ In this thesis we are going to first discuss the application of a copper hydride system, which was previously developed in our lab, to new Michael acceptors bearing a nitrogen group on the double bond. We are equally going to illustrate the development of a new cooperative dual catalysis strategy based on a CuI/Pd0 system. This strategy allowed us to successfully access α-allylated ketones diastereoselectively as well as enantioselectively.
In a later point, we are also going to examine the development of two synthetic pathways to generate unprecedented (NHC)CuI bifluoride complexes. We tested the activity of these complexes in several known CuI-catalyzed reactions, and consequently established the first CuI-catalyzed diastereoselective allylation of (R)-N-tert-butanesulfinyl aldimines. The method enables efficient, simple and general synthesis of enantiomerically enriched homoallylic amines at room temperature in high yields.
(CHIM 3) – UCL, 2013
Advisors/Committee Members: UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity, Riant, Olivier, Gohy, Jean-François, Elias, Benjamin, Poli, Giovanni, Gagosz, Fabien, Van Der Eycken, Johan.
Subjects/Keywords: Asymmetric catalysis; Copper(I); Palladium(0); Domino catalysis; Dual catalysis
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Export
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APA (6th Edition):
Nahra, F. (2013). Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions. (Thesis). Université Catholique de Louvain. Retrieved from http://hdl.handle.net/2078.1/133426
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):
Nahra, Fady. “Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions.” 2013. Thesis, Université Catholique de Louvain. Accessed March 04, 2021.
http://hdl.handle.net/2078.1/133426.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Nahra, Fady. “Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions.” 2013. Web. 04 Mar 2021.
Vancouver:
Nahra F. Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions. [Internet] [Thesis]. Université Catholique de Louvain; 2013. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/2078.1/133426.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Nahra F. Study of new reactions catalysed by copper(I) complexes : investigation of domino catalysis- and dual catalysis-type reactions. [Thesis]. Université Catholique de Louvain; 2013. Available from: http://hdl.handle.net/2078.1/133426
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Universitat de Valencia
12.
Miró Arenas, Javier.
New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
Degree: 2017, Universitat de Valencia
URL: http://hdl.handle.net/10550/58691
► A lo largo de las últimas décadas, los compuestos organofluorados han encontrado numerosas aplicaciones dentro del campo de las industrias farmacéutica y agroquímica, así como…
(more)
▼ A lo largo de las últimas décadas, los compuestos organofluorados han encontrado numerosas aplicaciones dentro del campo de las industrias farmacéutica y agroquímica, así como en ciencias de los materiales. Dadas las singulares propiedades del átomo de flúor, éste es capaz de inducir alteraciones significativas en propiedades físico-químicas de las moléculas como lipofilia, distribución de cargas, acidez-basicidad, capacidad de formar enlaces de hidrógeno e incluso, equilibrios conformacionales. Sin embargo, la presencia de flúor en productos naturales es escasa. De hecho, la gran mayoría de las moléculas orgánicas que contienen flúor son sintéticas. De ahí el gran interés por parte de la comunidad sintética en el desarrollo de nuevas metodologías para la introducción de flúor en moléculas orgánicas, bien sea mediante reacciones de fluoración selectivas sobre posiciones específicas de la molécula, o bien mediante el empleo de building blocks fluorados, y así construir la nueva molécula alrededor de estos sillares. En este contexto, en la presente tesis doctoral se describe el desarrollo de nuevas metodologías sintéticas catalizadas por complejos de metales de transición, estableciendo la química de flúor como el principal marco de aplicación de dichas metodologías.
En el capítulo 1 descubrimos que el 1,7-octadieno, líquido, puede actuar como fuente de etileno, gas, in situ mediante metátesis por cierre de anillo, estableciendo una estrategia complementaria a las condiciones de Mori. Esta metodología no sólo supone una ventaja operacional, sino que mejora la seguridad al evitar el uso de un gas inflamable como el etileno. La utilidad de esta metodología se ha ilustrado a través de una nueva reacción tándem multicomponente de metátesis cruzada de eninos-Diels Alder. Además, hemos podido validarla frente a las condiciones de Mori, obteniendo rendimientos comparables e incluso mejores en una secuencia de reacción análoga sobre cetonas y amidas gem-difluoropropargílicas.
En el capítulo 2 describimos la preparación de nuevas familias de heterociclos nitrogenados fluorados mediante catálisis con complejos de oro. A pesar del tremendo auge de la catálisis con complejos de oro a lo largo de la última década, el empleo de sustratos fluorados en este campo ha sido escaso. En nuestro grupo de investigación desarrollamos una nueva metodología para la preparación de aminas homopropargílicas fluoradas con buenos rendimientos, sustratos inexplorados en catálisis de oro. En este contexto y, de acuerdo con el carácter π-carbofílico exhibido por los complejos de oro, vislumbramos la posibilidad de acceder a distintos heterociclos nitrogenados mediante la modificación del “grupo protector” sobre el nitrógeno, desarrollando una reactividad diferencial. Así, cuando empleamos aril aminas, descubrimos una nueva reacción tándem de hidroaminación-aza-Diels Alder formal, dando lugar a esqueletos tetracíclicos presentes en productos naturales y difícilmente accesibles mediante otras metodologías. Un profundo estudio teórico del mecanismo de…
Advisors/Committee Members: Fustero Lardiés, Santos (advisor).
Subjects/Keywords: transition metal catalysis;
organofluorine chemistry;
metathesis;
gold catalysis;
palladium catalysis
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APA ·
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MLA ·
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CSE |
Export
to Zotero / EndNote / Reference
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APA (6th Edition):
Miró Arenas, J. (2017). New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
(Doctoral Dissertation). Universitat de Valencia. Retrieved from http://hdl.handle.net/10550/58691
Chicago Manual of Style (16th Edition):
Miró Arenas, Javier. “New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
” 2017. Doctoral Dissertation, Universitat de Valencia. Accessed March 04, 2021.
http://hdl.handle.net/10550/58691.
MLA Handbook (7th Edition):
Miró Arenas, Javier. “New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
” 2017. Web. 04 Mar 2021.
Vancouver:
Miró Arenas J. New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
[Internet] [Doctoral dissertation]. Universitat de Valencia; 2017. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/10550/58691.
Council of Science Editors:
Miró Arenas J. New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
[Doctoral Dissertation]. Universitat de Valencia; 2017. Available from: http://hdl.handle.net/10550/58691
RMIT University
13.
Kar, G.
Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes.
Degree: 2012, RMIT University
URL: http://researchbank.rmit.edu.au/view/rmit:161366
► The halide-bridged cyclopalladated complexes [Pd2(m-X)2(k2-2-C6F4PPh2)2] (X = Cl, Br) were prepared in high yields from the reaction of equimolar amounts of 2-Me3SnC6F4PPh2 and [PdX2(cod)] (cod…
(more)
▼ The halide-bridged cyclopalladated complexes [Pd2(m-X)2(k2-2-C6F4PPh2)2] (X = Cl, Br) were prepared in high yields from the reaction of equimolar amounts of 2-Me3SnC6F4PPh2 and [PdX2(cod)] (cod = 1,5-cyclooctadiene). These complexes are not thermodynamically stable and slowly dimerise in solution over several days to give tetranuclear [Pd4(m-X)4(m-2-C6F4PPh2)4] in which the four 2-C6F4PPh2 groups bridge two pairs of palladium atoms. Attempts to prepare protio analogues of the dinuclear complexes by treating [PdX2(cod)] (X = Cl, Br) with 2-Me3SnC6H4PPh2 gave [Pd4(m-X)4(m-2-C6H4PPh2)4] as the only isolable product. Anation of [Pd2(m-X)2(k2-2-C6F4PPh2)2] with the appropriate alkali metal or silver salt gave the corresponding iodo-, acetato-, benzoato- and thiocyanato-complexes which are also unstable with respect to ring-opening reactions. For example, heating a solution of [Pd2(m-SCN)2(k2-2-C6F4PPh2)2] gave [Pd4(m-SCN)4(k2-2-C6F4PPh2)2(m-2-C6F4PPh2)2] in which only two of the four chelate rings are opened, and solutions of [Pd2(m-OAc)2(k2-2-C6F4PPh2)2] rearranged to give [Pd2(m-OAc)2(m-2-C6F4PPh2)2]. The halide bridges in [Pd2(m-X)2(k2-2-C6F4PPh2)2] (X = Cl, Br) are cleaved by acetone and THF with retention of the chelate rings to give species tentatively identified as [PdX(solvent)(k2-2-C6F4PPh2)]; evaporation of the solvent in vacuo regenerated the original dimers. In contrast, irreversible ring opening occurs in acetonitrile, the products being [Pd2X2(NCMe)2(m-2-C6F4PPh2)2]. Reaction of [Pd2(m-Br)2(k2-2-C6F4PPh2)2] with [Na(acac)] gives initially monomeric [Pd(acac)(k2-2-C6F4PPh2)], which dimerises by chelate ring-opening in dichloromethane/methanol to [Pd2(acac)2(µ-2-C6F4PPh2)2]. The tertiary phosphines L react with [Pd2(m-Br)2(k2-2-C6F4PPh2)2] to give monomeric complexes [PdBr(k2-2-C6F4PPh2)L] (L = PPh3, PPh2Fc); both these and the derived iodo-complexes exist as cis/trans isomers in solution (predominantly trans in non-polar solvents, predominantly cis in acetonitrile). The reduction of many of these 2-C6F4PPh2 compounds has been studied by cyclic voltammetry and rotating disk electrochemical techniques in dichloromethane and acetonitrile. The results indicate that, in the first step, one electron is added to each metal atom to generate a transient palladium(I) species. Corresponding 2-C6H4PPh2 complexes are reduced at higher potentials (by ca. 0.4 V) and the course of the reduction could not be defined. However, attempts to detect the known dipalladium(I) complex [Pd2(µ-2-C6F4PPh2)2(PPh3)2] by controlled potential reduction of [PdBr(k2-2-C6F4PPh2)(PPh3)] failed, possibly due to over-reduction. Ill defined products with complex 31P NMR spectra were obtained, these possibly being palladium(0) clusters. Cyclic voltammetry of [PdX(k2-2-C6F4PPh2)(PPh2Fc)] (X = Br, I) led initially to the mono-cation which rapidly released [PPh2Fc]+ by cleavage of the Pd-P bond. The voltammetric behaviour of [PPh2Fc]+ is considerably more complex than that of ferrocenium and probably involves oxidation at the…
Subjects/Keywords: Fields of Research; Palladium; cyclometallation; electrochemistry; catalysis
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APA ·
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MLA ·
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CSE |
Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Kar, G. (2012). Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes. (Thesis). RMIT University. Retrieved from http://researchbank.rmit.edu.au/view/rmit:161366
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):
Kar, G. “Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes.” 2012. Thesis, RMIT University. Accessed March 04, 2021.
http://researchbank.rmit.edu.au/view/rmit:161366.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Kar, G. “Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes.” 2012. Web. 04 Mar 2021.
Vancouver:
Kar G. Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes. [Internet] [Thesis]. RMIT University; 2012. [cited 2021 Mar 04].
Available from: http://researchbank.rmit.edu.au/view/rmit:161366.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Kar G. Synthesis, structure, electrochemical and catalytic behaviour of new cyclopalladated complexes. [Thesis]. RMIT University; 2012. Available from: http://researchbank.rmit.edu.au/view/rmit:161366
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of California – Irvine
14.
Hirner, Joshua J.
Dual-Metal and Metaloid Reactivity with Gold(I).
Degree: Chemical and Material Physics, 2014, University of California – Irvine
URL: http://www.escholarship.org/uc/item/7qv8v3ds
► Chapter 1. This chapter provides a very brief introduction to the field of homogeneous gold(I) catalysis and discusses the context of the Blum group's previous…
(more)
▼ Chapter 1. This chapter provides a very brief introduction to the field of homogeneous gold(I) catalysis and discusses the context of the Blum group's previous studies in this area.Chapter 2: Organogold compounds undergo stoichiometric cross-coupling reactions with aryl and vinyl bromides in high yield under mild, nickel-catalyzed conditions. The reaction tolerates both electron-rich and electron-poor organogold complexes, and vinyl bromides undergo cross-coupling with high stereoselectivity. This novel transformation links well-established nickel catalysis with more recent developments in organogold transformations.Chapter 3: A vinyl aziridine activation strategy cocatalyzed by Pd(0) and a Au(I) Lewis acid was developed. This rearrangement installs a C-C and a C-N bond in one synthetic step to form pyrrolizidine and indolizidine products. Two proposed mechanistic roles for the gold cocatalyst were considered: (1) carbophilic gold catalysis or (2) azaphilic gold catalysis. Mechanistic studies support an azaphilic Lewis acid activation of the aziridine over a carbophilic Lewis acid activation of the alkene.Chapter 4: A borylation reaction cocatalyzed by Au and Rh was proposed as a means of isolating catalytic organogold intermediates as the corresponding organoboron derivatives for use in subsequent functionalization steps. Products consistent with the proposed reactivity were obtained, but control experiments indicated no role for Rh in the reaction; organogold complexes were found to undergo facile thermal reactivity with electrophilic B without Rh. Electronic effects in the chemoselective borylation of heterocyclic organogold complexes were studied, suggesting design parameters used in the development of the Au-catalyzed borylation reactions discussed in Chapters 5 and 6.Chapter 5: For nearly 70 years, the addition of boron-X sigma bonds to carbon-carbon multiple bonds has been employed in the preparation of organoboron reagents. However, the significantly higher strength of boron-oxygen bonds has thus far precluded their activation for addition, preventing a direct route to access a potentially valuable class of oxygen-containing organoboron reagents for divergent synthesis. Herein is discussed an alkoxyboration reaction, the addition of boron-oxygen sigma bonds to alkynes. Functionalized O-heterocyclic boronic acid derivatives are produced using this transformation, which is mild and exhibits broad functional group compatibility. Our results demonstrate activation of this boron-oxygen bond using a gold catalysis strategy that is fundamentally different from that used previously for other boron addition reactions.Chapter 6: Four additional investigations stemming from the benzofuran-forming alkoxyboration reaction (Chapter 5) are described. Discussed are electronic effects in the B/Au transmetalation reaction, progress towards an intermolecular alkoxyboration reaction, and the expansion of the alkoxyboration concept to two additional substrate classes for intramolecular B-O sigma-bond activation reactivity.
Subjects/Keywords: Chemistry; boron; catalysis; gold; nickel; palladium
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APA (6th Edition):
Hirner, J. J. (2014). Dual-Metal and Metaloid Reactivity with Gold(I). (Thesis). University of California – Irvine. Retrieved from http://www.escholarship.org/uc/item/7qv8v3ds
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):
Hirner, Joshua J. “Dual-Metal and Metaloid Reactivity with Gold(I).” 2014. Thesis, University of California – Irvine. Accessed March 04, 2021.
http://www.escholarship.org/uc/item/7qv8v3ds.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Hirner, Joshua J. “Dual-Metal and Metaloid Reactivity with Gold(I).” 2014. Web. 04 Mar 2021.
Vancouver:
Hirner JJ. Dual-Metal and Metaloid Reactivity with Gold(I). [Internet] [Thesis]. University of California – Irvine; 2014. [cited 2021 Mar 04].
Available from: http://www.escholarship.org/uc/item/7qv8v3ds.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Hirner JJ. Dual-Metal and Metaloid Reactivity with Gold(I). [Thesis]. University of California – Irvine; 2014. Available from: http://www.escholarship.org/uc/item/7qv8v3ds
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
UCLA
15.
Fan, Yi Chiao.
Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products.
Degree: Chemistry, 2015, UCLA
URL: http://www.escholarship.org/uc/item/5wf238tv
► In Chapter 1, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides…
(more)
▼ In Chapter 1, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis.In Chapter 2, we prepared oxazolidines through 1,3-bis(diphenylphosphino)-propane (DPPP)–catalyzed mixed double-Michael reactions of β-amino alcohols with electron-deficient acetylenes. These reactions are very suitable for the diversity-oriented parallel syntheses of oxazolidines because: (i) they are performed under mild metal-free conditions and (ii) the products are isolated without complicated work-up. To demonstrate the applicability of mixed double-Michael reactions for the preparation of five-membered-ring heterocycles, we prepared 60 distinct oxazolidines from five β-amino alcohols and 12 electron-deficient acetylenes. We synthesized 36 of these 60 oxazolidines in enantiomerically pure form from proteinogenic amino acid–derived β-amino alcohols.In Chapter 3, we used sequential catalysis—PPh3-catalyzed nucleophilic addition followed by Pd(0)-catalyzed Heck cyclization—to construct complex functionalized alkylidene phthalans rapidly, in high yields, and with good stereoselectivities (E/Z ratios of up to 1:22). The scope of this Michael–Heck reaction includes substrates bearing various substituents around the alkylidene phthalan backbone. Applying this efficient sequential catalysis, we accomplished concise total syntheses of 3-deoxyisoochacinic acid, isoochracinic acid, and isoochracinol.In Chapter 4, densely functionalized alkylidene indanes and indanones can be prepared efficiently in one pot, in high yields with good stereoselectivities (in some cases exclusively the Z-isomer), through a route involving phosphine-catalyzed Michael addition followed by palladium-catalyzed Heck cyclization. These transformations tolerate substrates bearing various substituents around the indane/indanone motif. Employing this technology, a concise formal synthesis of sulindac, a non-steroidal anti-inflammatory drug, has been established.
Subjects/Keywords: Chemistry; Michael–Heck; Palladium; Phosphine; Tandem Catalysis
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APA (6th Edition):
Fan, Y. C. (2015). Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products. (Thesis). UCLA. Retrieved from http://www.escholarship.org/uc/item/5wf238tv
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):
Fan, Yi Chiao. “Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products.” 2015. Thesis, UCLA. Accessed March 04, 2021.
http://www.escholarship.org/uc/item/5wf238tv.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Fan, Yi Chiao. “Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products.” 2015. Web. 04 Mar 2021.
Vancouver:
Fan YC. Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products. [Internet] [Thesis]. UCLA; 2015. [cited 2021 Mar 04].
Available from: http://www.escholarship.org/uc/item/5wf238tv.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Fan YC. Tandem Phosphine–Palladium Catalysis and Total Syntheses of Natural Products. [Thesis]. UCLA; 2015. Available from: http://www.escholarship.org/uc/item/5wf238tv
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Utah
16.
Werner, Erik Winters.
Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts.
Degree: PhD, Chemistry, 2012, University of Utah
URL: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/1939/rec/684
► The Heck reaction is an important tool in target-directed syntheses, but its fullpotential has yet to be realized due to limited substrate compatibility. This limitationarises…
(more)
▼ The Heck reaction is an important tool in target-directed syntheses, but its fullpotential has yet to be realized due to limited substrate compatibility. This limitationarises from poor behavior of the selectivity-determining steps of migratory insertion and -hydride elimination when using electronically nonbiased substrates. The inability toaccommodate nonbiased alkenes is due to chemist's poor understanding of thecontrolling factors in these two key mechanistic steps. Herein are described Pd0 and PdIIcatalysts that exhibit unique selectivity in these electronically nonbiased molecularsystems.Chapter 1 describes the use of an electrophilic PdII catalyst to install two identicalaryl groups upon terminal aliphatic olefins. The use of the same system, with a differentaryl source, led to the discovery that electrophilic PdII catalysts are capable of selectivelydelivering (E)-styrenyl products from electronically nonbiased olefins.Chapter 2 details optimization of the PdII system to selectively delivertraditionally inaccessible (E)-styrenyl products, and evaluation of substrate scope.Mechanistic experiments are performed, suggesting that the unique selectivity observedis attributable to the cationic nature of the catalyst, that the ligand on Pd is required forcatalyst stability, and that the catalyst distinguishes between B-hydrogens on the basis ofC-H bond strength. These findings are applied to rational design of a Pd0-catalyzedHeck reaction of similar substrates.The Pd0-catalyzed system exhibits greater functional group tolerance than theoxidative system, is operationally simple, and requires no added stabilizing ligand. Thedesign and study of this reaction is the subject of Chapter 3. Mechanistic studies suggestthat solvent choice is crucial in allowing the metal center to distinguish between -hydrogens on the basis of their relative hydridic nature.The insight gained in the work described in Chapters 2 and 3 allowed for therational design of a system enabling enantioselective Heck reactions using acyclicsubstrates. This methodology, described in Chapter 4, was intended to deliver opticallyactive -aryl ketones from allylic alcohol substrates. After establishing that the reactionperforms as anticipated, it was applied to the unprecedented single-step enantioselectivesynthesis of y-aryl ketones, and aldehydes, and a d-aryl aldehyde.
Subjects/Keywords: Catalysis; Enantioselective; Heck; Palladium; Selective; Styrene
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APA (6th Edition):
Werner, E. W. (2012). Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts. (Doctoral Dissertation). University of Utah. Retrieved from http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/1939/rec/684
Chicago Manual of Style (16th Edition):
Werner, Erik Winters. “Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts.” 2012. Doctoral Dissertation, University of Utah. Accessed March 04, 2021.
http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/1939/rec/684.
MLA Handbook (7th Edition):
Werner, Erik Winters. “Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts.” 2012. Web. 04 Mar 2021.
Vancouver:
Werner EW. Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts. [Internet] [Doctoral dissertation]. University of Utah; 2012. [cited 2021 Mar 04].
Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/1939/rec/684.
Council of Science Editors:
Werner EW. Development and evaluation of reactions utilizing uniquely selective electrophilic Pd catalysts. [Doctoral Dissertation]. University of Utah; 2012. Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/1939/rec/684
University of Utah
17.
Saini, Vaneet.
Palladium-catalyzed difunctionalization reactions of ethylene and dienes.
Degree: PhD, Chemistry, 2015, University of Utah
URL: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3943/rec/1791
► During the past few decades, one-pot multicomponent reactions have attracted significant attention because of their ability to install multiple carbon-carbon or carbonheteroatom bonds in a…
(more)
▼ During the past few decades, one-pot multicomponent reactions have attracted significant attention because of their ability to install multiple carbon-carbon or carbonheteroatom bonds in a single step. However, the development of these reactions is a challenge because of the generation of many side products arising from undesired reaction pathways. Hence, optimization for the formation of desired products is difficult. Our group has been involved in developing such multicomponent reactions that take advantage of the stability of π-allyl/benzyl palladium species to generate biologically relevant and synthetically challenging products in an efficient manner. Herein, I describe the development of three novel multicomponent transformations to achieve difunctionalization of cheap olefins such as ethylene and dienes. First, a Pd(II)-catalyzed three-component coupling involving ethylene, alkenyl triflates, and aryl boronic acids is described, where 1,1-vinylarylated products can be obtained in high yields and good to high selectivity. The crucial factor for an efficientreaction is cationic Pd(II)-intermediates, which prevent side products such as Suzuki products and Heck products. In general, the scope of the reaction is good as both electronrich and electron-withdrawing boronic acids are tolerated. Heteroaromatic cross-couplingpartners are also compatible under the reaction conditions. However, the scope is limited to six-membered alkenyl electrophiles, which bias the selectivity towards the formation of 1,1-vinylarylated products.Second, the scope of this three-component reaction was extended to aryl electrophiles such as aryl diazonium salts. The reaction can also be used to couple allyliccarbonates as the olefin source instead of ethylene to afford a wider range of 1,1-diarylalkanes. Also, deuterium labeling study and cross-over experiment revealed usefulinformation regarding the mechanistic aspect of the reaction.Finally, 1,2-hydrovinylation of terminal 1,3-dienes was achieved with alkenyl triflates/nonaflates and a hydride source. The reaction can be used to couple a variety oftriflates derived from natural products to generate complex molecules in a mild fashion.Additionally, configurationally-defined alkenyl triflates (i.e., E/Z) can be coupled efficiently to generate synthetically useful tri- and tetrasubstituted alkenes.
Subjects/Keywords: Alkenes; Catalysis; Dienes; Difunctionalization; Ethylene; Palladium
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APA (6th Edition):
Saini, V. (2015). Palladium-catalyzed difunctionalization reactions of ethylene and dienes. (Doctoral Dissertation). University of Utah. Retrieved from http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3943/rec/1791
Chicago Manual of Style (16th Edition):
Saini, Vaneet. “Palladium-catalyzed difunctionalization reactions of ethylene and dienes.” 2015. Doctoral Dissertation, University of Utah. Accessed March 04, 2021.
http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3943/rec/1791.
MLA Handbook (7th Edition):
Saini, Vaneet. “Palladium-catalyzed difunctionalization reactions of ethylene and dienes.” 2015. Web. 04 Mar 2021.
Vancouver:
Saini V. Palladium-catalyzed difunctionalization reactions of ethylene and dienes. [Internet] [Doctoral dissertation]. University of Utah; 2015. [cited 2021 Mar 04].
Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3943/rec/1791.
Council of Science Editors:
Saini V. Palladium-catalyzed difunctionalization reactions of ethylene and dienes. [Doctoral Dissertation]. University of Utah; 2015. Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3943/rec/1791
University of Alberta
18.
Sun, Ho-Yan.
Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes.
Degree: PhD, Department of Chemistry, 2015, University of Alberta
URL: https://era.library.ualberta.ca/files/pk02cd596
► Synthetic organic chemistry is an area that has seen incredible growth through the years. The level of molecular complexity that can be achieved through available…
(more)
▼ Synthetic organic chemistry is an area that has seen
incredible growth through the years. The level of molecular
complexity that can be achieved through available synthetic methods
today is remarkable. Still, as the field continues to progress,
increasing focus is being placed upon the strategic development of
methods that are both efficient and selective in order to allow for
the rapid assembly of molecular complexity. In this regard,
organoboron reagents represent a class of compounds that have
demonstrated great synthetic diversity. These compounds have been
applied, through a range of methods, in the efficient construction
of C-heteroatom and C-C bonds. Arguably among some of the most
frequently used processes is the Suzuki-Miyaura cross-coupling.
Since its conception, this reaction has been widely applied in a
broad range of fields including, but not limited to, the
pharmaceutical and materials industries. To date, the application
of the Suzuki-Miyaura cross-coupling to the construction of sp2-sp2
bond connections has been extensively studied and many groups are
now directing efforts towards employing this method for the
construction of stereogenic centres. To this end, this thesis
details studies in developing catalytic stereoselective
Suzuki-Miyaura reactions for the cross-coupling of sp3-hybridized
organoboronates for the efficient construction of stereogenic
carbon centres. In order to demonstrate the versatility of
optically enriched diboronyl compounds, Chapter 2 describes the
development of an iterative cross-coupling process to transform
3,3-diboronylamides into the corresponding diarylmethanes – a motif
that is commonly found in pharmaceutically relevant compounds. In
addition, studies were made to determine the stereochemical outcome
of the cross-coupling reaction. As a progression from the
cross-coupling of optically enriched secondary boronates, Chapter 3
describes the development of an asymmetric Suzuki-Miyaura
cross-coupling reaction for the desymmetrization of prochiral
1,1-diboronylalkanes. Ligand optimization in combination with
mechanistic studies on the role of the base led to reaction
conditions that produced optically enriched secondary
organoboronates in good yields and enantioselectively. The details
of the reaction scope and scalability will also be discussed. Due
to the synthetic value demonstrated by 1,1-diboronyl compounds, an
extension of these cross-coupling methods to 1,1,1-triboronylated
compounds is desirable, as this would represent a unique way to
construct complex stereogenic centres. In Chapter 4, initial
studies on the synthesis of 1,1,1-triboronyl alkanes will be
described. Given their similar potential as a synthetic handle for
the construction of stereogenic centres, the development of a
method that produces 3,3-diboronyl 3-silyl ketones as the products
will also be discussed.
Subjects/Keywords: Suzuki-Miyaura; organoboronates; stereoselective couplings; palladium; catalysis
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APA ·
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MLA ·
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CSE |
Export
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Manager
APA (6th Edition):
Sun, H. (2015). Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes. (Doctoral Dissertation). University of Alberta. Retrieved from https://era.library.ualberta.ca/files/pk02cd596
Chicago Manual of Style (16th Edition):
Sun, Ho-Yan. “Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes.” 2015. Doctoral Dissertation, University of Alberta. Accessed March 04, 2021.
https://era.library.ualberta.ca/files/pk02cd596.
MLA Handbook (7th Edition):
Sun, Ho-Yan. “Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes.” 2015. Web. 04 Mar 2021.
Vancouver:
Sun H. Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes. [Internet] [Doctoral dissertation]. University of Alberta; 2015. [cited 2021 Mar 04].
Available from: https://era.library.ualberta.ca/files/pk02cd596.
Council of Science Editors:
Sun H. Breaking New Ground with the Suzuki-Miyaura Reaction:
Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes. [Doctoral Dissertation]. University of Alberta; 2015. Available from: https://era.library.ualberta.ca/files/pk02cd596
Penn State University
19.
Nack, William Andrew.
N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization.
Degree: 2016, Penn State University
URL: https://submit-etda.libraries.psu.edu/catalog/p5547r37h
► Saturated N-heterocycles are useful motifs in medicinal chemistry, but their application often hinges on limited synthetic methods. We have developed a strategy for the synthesis…
(more)
▼ Saturated N-heterocycles are useful motifs in medicinal chemistry, but their application often hinges on limited synthetic methods. We have developed a strategy for the synthesis of the N-heterocycle 1,2,3,4-tetrahydroquinoline (THQ) using Pd-catalyzed C–H functionalization reactions. Beginning from an alkyl picolinamide, a picolinic acid (PA)-directed, Pd-catalyzed sp3 C–H arylation reaction yields a 3-arylpropylpicolinamide intermediate. This intermediate is then cyclized via a sequence of ortho sp2 C–H iodination followed by C–N cross coupling. We explored two methods for this critical iodination: a directed electrophilic aromatic substitution (EAS) method, and a Pd-catalyzed C–H iodination reaction. To demonstrate the scope of this strategy, a variety of substituted THQ scaffolds were synthesized, including (+)-angustureine. Finally, a mechanistic hypothesis for the directed EAS reaction is presented, integrating results from the recent literature with our own preliminary mechanistic studies.
In the second chapter, a room temperature diastereoselective Pd-catalyzed C–H arylation reaction of 8-aminoquinoline (AQ) coupled cycloalkane carboxylic acids is described. Pd-catalyzed bidentate-auxiliary directed C–H arylation has been applied extensively for the synthesis of aryl cycloalkane moieties of natural products. We developed an improved room temperature protocol for cycloalkane C–H arylation and explored its scope. Further C–H functionalization reactions of the arylated products have been examined, and a mechanistic hypothesis is put forth which rationalizes the diastereoselectivity of the reaction, as well as observed reactivity trends.
Advisors/Committee Members: Gong Chen, Dissertation Advisor/Co-Advisor, Gong Chen, Committee Chair/Co-Chair, Alexander Radosevich, Committee Member, Kenneth Feldman, Committee Member, Charles Anderson, Outside Member.
Subjects/Keywords: C-H Functionalization; Palladium; Catalysis; Heterocycles
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APA (6th Edition):
Nack, W. A. (2016). N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization. (Thesis). Penn State University. Retrieved from https://submit-etda.libraries.psu.edu/catalog/p5547r37h
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):
Nack, William Andrew. “N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization.” 2016. Thesis, Penn State University. Accessed March 04, 2021.
https://submit-etda.libraries.psu.edu/catalog/p5547r37h.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Nack, William Andrew. “N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization.” 2016. Web. 04 Mar 2021.
Vancouver:
Nack WA. N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization. [Internet] [Thesis]. Penn State University; 2016. [cited 2021 Mar 04].
Available from: https://submit-etda.libraries.psu.edu/catalog/p5547r37h.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Nack WA. N-Heterocycle Synthesis via Bidentate-Auxiliary Directed Remote C-H Functionalization. [Thesis]. Penn State University; 2016. Available from: https://submit-etda.libraries.psu.edu/catalog/p5547r37h
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Newcastle
20.
Setiawan, Adi.
Catalytic combustion of ventilation air methane released from coal mines.
Degree: PhD, 2015, University of Newcastle
URL: http://hdl.handle.net/1959.13/1312733
► Research Doctorate - Doctor of Philosophy (PhD)
This thesis presents a series of investigation on catalytic combustion of lean methane mixtures emitted from coal mine…
(more)
▼ Research Doctorate - Doctor of Philosophy (PhD)
This thesis presents a series of investigation on catalytic combustion of lean methane mixtures emitted from coal mine ventilation air. The study involves catalyst preparation, catalytic activity and stability evaluation under simulated ventilation air methane (VAM) gas, and understanding the catalyst deactivation phenomena. The investigation on the chemical and physical properties of catalysts employed a number of techniques including nitrogen physisorption, hydrogen chemisorption, temperature-programmed desorption (TPD), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronic microscopy and X-ray photoelectron spectroscopy (XPS) analyses. Investigation on the influence of pre-treatment conditions on Pd/Al₂O₃catalysts discloses significant differences in the light off temperatures and the extent of coke deposition, depending on whether the catalysts were pre-treated under oxidising or reducing conditions. The oxidised palladium catalysts were reduced by methane under reaction conditions and exhibited similar activity compared to catalysts which were activated under hydrogen. The long-term stability tests of the catalysts prepared for this study suggest that the primary factor responsible for low temperature catalyst deactivation is the water vapour present in the feed stream. Although no palladium hydroxide phase was observed during short-term experiment, extended exposure to wet feed results in the formation of palladium hydroxide, which appears to match the progressive deactivation of the Pd/Al₂O₃catalyst. Introducing VAM dust causes a variation in catalytic activity originating from coal-dust ignition and the effect of chloride on the surface of the catalyst. Nevertheless, in the presence of inhibiting agents, an average methane conversion of higher than 75 % over 1,100 h was achieved at reaction temperatures below 600 ºC. Although supported Pd catalysts are higher in activity, nano-sized Co₃O₄catalysts exhibit excellent stability. No changes in oxidation/chemical states were observed from the Co₃O₄catalyst after time on stream experiments. In contrast, the presence of strongly bonded hydroxyl species on the surface of Fe₂O₃catalysts highlights the role of water vapour in catalyst deactivation. Oxygen TPD shows that higher oxygen surface coverage of Co₃O₄is suggested to be responsible for a higher activity in comparison with Fe₂O₃catalysts. Co-precipitating gold particles with cobalt oxide or iron oxide does not enhance the activity of the catalyst, which is most likely due to blocking the active site of support by the gold particles. Enhanced hydrothermal stability was observed over a novel Pd/TS-1 catalyst during 1,900 h time-on-stream experiments, where a 90 % methane conversion level was successfully maintained at temperature < 500 °C. Surface oxygen mobility and coverage plays a major role for the activity and stability of this catalyst in the presence of a large excess of water. It was identified that water adsorption and…
Advisors/Committee Members: University of Newcastle. Faculty of Engineering & Built Environment, School of Engineering.
Subjects/Keywords: methane; combustion; catalysis; palladium; thesis by publication
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APA (6th Edition):
Setiawan, A. (2015). Catalytic combustion of ventilation air methane released from coal mines. (Doctoral Dissertation). University of Newcastle. Retrieved from http://hdl.handle.net/1959.13/1312733
Chicago Manual of Style (16th Edition):
Setiawan, Adi. “Catalytic combustion of ventilation air methane released from coal mines.” 2015. Doctoral Dissertation, University of Newcastle. Accessed March 04, 2021.
http://hdl.handle.net/1959.13/1312733.
MLA Handbook (7th Edition):
Setiawan, Adi. “Catalytic combustion of ventilation air methane released from coal mines.” 2015. Web. 04 Mar 2021.
Vancouver:
Setiawan A. Catalytic combustion of ventilation air methane released from coal mines. [Internet] [Doctoral dissertation]. University of Newcastle; 2015. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/1959.13/1312733.
Council of Science Editors:
Setiawan A. Catalytic combustion of ventilation air methane released from coal mines. [Doctoral Dissertation]. University of Newcastle; 2015. Available from: http://hdl.handle.net/1959.13/1312733
University of Johannesburg
21.
Thompson, Catharine.
A structural study of palladium complexes containing hemilabile ligands.
Degree: 2012, University of Johannesburg
URL: http://hdl.handle.net/10210/7092
► D.Phil.
Palladium chemistry has advanced dramatically in the last few years, with a huge number of wide-ranging studies, particularly with respect to the application of…
(more)
▼ D.Phil.
Palladium chemistry has advanced dramatically in the last few years, with a huge number of wide-ranging studies, particularly with respect to the application of palladium complexes as catalysts, having been performed. The discovery of the phenomenon of hemilability (the ability of a ligand to be bidentately coordinated but with one donor atom more weakly bound and thus able to decoordinate in the presence of a catalytic substrate) has further assisted the growth, since it has allowed a greater understanding of the mechanisms of catalytic-reactions. However, the focus of much of this work has been on ligands containing phosphorus and oxygen as potential donor atoms, with little attention being turned to ligands with other donor atoms. The current study concentrates on a series of palladium complexes containing potentially hemilabile thioether, selenoether and telluroether carboxylate ligands with the oxygen as the strongly coordinating atom. Each complex was completed by the palladium coordinating to a phenyl ligand trans to the oxygen of the hemilabile ligand and either one or two triphenylphosphine ligands, depending on whether or not the -hemilabile ligand was monodentately or bidentately coordinated. These complexes are of interest as possible catalysts for the oligomerisation of ethene, and had been previously synthesised and characterised by NMR spectroscopy, mass spectrometry and catalytic studies. In the current work the crystal and molecular structures of the various complexes were determined. Since a number of pairs of complexes containing the monodentate and bidentate forms of the ligands were identified the hemilability of the ligands was confirmed.
Subjects/Keywords: Palladium compounds; Chemical reactions; Ligands; Catalysis; Catalysts
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APA (6th Edition):
Thompson, C. (2012). A structural study of palladium complexes containing hemilabile ligands. (Thesis). University of Johannesburg. Retrieved from http://hdl.handle.net/10210/7092
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):
Thompson, Catharine. “A structural study of palladium complexes containing hemilabile ligands.” 2012. Thesis, University of Johannesburg. Accessed March 04, 2021.
http://hdl.handle.net/10210/7092.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Thompson, Catharine. “A structural study of palladium complexes containing hemilabile ligands.” 2012. Web. 04 Mar 2021.
Vancouver:
Thompson C. A structural study of palladium complexes containing hemilabile ligands. [Internet] [Thesis]. University of Johannesburg; 2012. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/10210/7092.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Thompson C. A structural study of palladium complexes containing hemilabile ligands. [Thesis]. University of Johannesburg; 2012. Available from: http://hdl.handle.net/10210/7092
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Toronto
22.
Caulford Menzies, Perry Jacob.
Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides.
Degree: 2014, University of Toronto
URL: http://hdl.handle.net/1807/74595
► Pd catalyzed cross coupling reactions are extensively used to effect a multitude of organic transformations. The recent advent of carbon-halogen reversible oxidative addition has introduced…
(more)
▼ Pd catalyzed cross coupling reactions are extensively used to effect a multitude of organic transformations. The recent advent of carbon-halogen reversible oxidative addition has introduced C-X bond forming as a viable catalytic process. These carbohalogenation reactions are ideal because the reactive halide functionalities are retained in the products, however several limitations in the methodology still remain. Specifically, carbohalogenations using aryl bromides and chlorides and the formation of vinyl halide products are desirable transformations that have been elusive.
Cyclopropene substrates were initially examined as intermolecular carbohalogenation coupling partners but these substrates were not found to be amenable to carbohalogenation. The focus shifted to using alkynes as intramolecular coupling partners. These substrates were found to successfully undergo cyclization, forming vinyl halide products. Additionally, aryl iodides, bromides and chlorides all react to form the corresponding vinyl halides. The reaction parameters were examined, a substrate scope was developed and mechanistic studies were performed.
M.Sc.
2016-11-18 00:00:00
Advisors/Committee Members: Lautens, Mark, Chemistry.
Subjects/Keywords: Carbohalogenation; Catalysis; Palladium; Steric Bulk; 0485
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APA (6th Edition):
Caulford Menzies, P. J. (2014). Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides. (Masters Thesis). University of Toronto. Retrieved from http://hdl.handle.net/1807/74595
Chicago Manual of Style (16th Edition):
Caulford Menzies, Perry Jacob. “Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides.” 2014. Masters Thesis, University of Toronto. Accessed March 04, 2021.
http://hdl.handle.net/1807/74595.
MLA Handbook (7th Edition):
Caulford Menzies, Perry Jacob. “Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides.” 2014. Web. 04 Mar 2021.
Vancouver:
Caulford Menzies PJ. Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides. [Internet] [Masters thesis]. University of Toronto; 2014. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/1807/74595.
Council of Science Editors:
Caulford Menzies PJ. Palladium-catalyzed Carbohalogenation of Sterically Congested Alkynes: An Intramolecular Approach to the Synthesis of Vinyl Halides. [Masters Thesis]. University of Toronto; 2014. Available from: http://hdl.handle.net/1807/74595
Victoria University of Wellington
23.
Fisk, Matthew.
Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade.
Degree: 2017, Victoria University of Wellington
URL: http://hdl.handle.net/10063/6742
► The design and development of new chemical reactions is crucial for progress in organic synthesis research. Cascade reactions, involving two or more steps carried out…
(more)
▼ The design and development of new chemical reactions is crucial for progress in organic synthesis research. Cascade reactions, involving two or more steps carried out in situ in a single pot, provide a step-efficient and atom-economic route to synthesise polycyclic ring systems. The synthesis of new heterocyclic ring systems provides valuable routes towards complex natural products. Previous work in the Harvey group led to the development of a regioselective
palladium-catalysed allylic alkylation (Pd-AA) cascade. This research aims to expand the scope and utility of this existing Pd-AA cascade, by optimising the current reaction conditions and exploring a range of non-symmetric pyran-based bis-electrophiles and nitrogen and sulfur-based β-carbonyl bis-nucleophiles.
Isomeric 2,3-unsaturated silyl glycosides based on D-glucose and D-galactose were successfully synthesised. These substrates were assessed as bis-electrophiles in the Pd-AA cascade. The yield of the cascade was successfully optimised with the glucose-derived substrate 4-hydroxy-6-methylpyran-2-one, using Pd₂(dba)₃ and Xantphos, to 87% from the previously reported 77% yield. However, the galactose-derived silyl glycoside formed an undesired pyranone as the major product. Additionally, a series of β-dicarbonyl compounds (4-hydroxy-6-methylpyran-2-one analogues) were assessed as bis-nucleophiles in the Pd-AA cascade, with all of the analogues forming complex mixtures of side products and a fully unsaturated pyranone as the major isolated product.
Advisors/Committee Members: Harvey, Joanne.
Subjects/Keywords: Palladium Catalysis; Allylic Substitution; Silyl glycoside
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MLA ·
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Export
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APA (6th Edition):
Fisk, M. (2017). Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade. (Masters Thesis). Victoria University of Wellington. Retrieved from http://hdl.handle.net/10063/6742
Chicago Manual of Style (16th Edition):
Fisk, Matthew. “Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade.” 2017. Masters Thesis, Victoria University of Wellington. Accessed March 04, 2021.
http://hdl.handle.net/10063/6742.
MLA Handbook (7th Edition):
Fisk, Matthew. “Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade.” 2017. Web. 04 Mar 2021.
Vancouver:
Fisk M. Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade. [Internet] [Masters thesis]. Victoria University of Wellington; 2017. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/10063/6742.
Council of Science Editors:
Fisk M. Optimisation and Scope of a Palladium-Catalysed Allylic Alkylation Cascade. [Masters Thesis]. Victoria University of Wellington; 2017. Available from: http://hdl.handle.net/10063/6742
Université Catholique de Louvain
24.
Soetens, Mathieu.
Development of transition metal catalysts for bioorthogonal reactions.
Degree: 2019, Université Catholique de Louvain
URL: http://hdl.handle.net/2078.1/216769
► Cancer is a metabolic disease characterized by immortal cells which develop in a non-controlled and anarchic fashion after undergoing mutations and alterations in their DNA.…
(more)
▼ Cancer is a metabolic disease characterized by immortal cells which develop in a non-controlled and anarchic fashion after undergoing mutations and alterations in their DNA. These cells tend to grow in masses which are called tumours. It has emerged as one of the ten main causes of mortality along with cardiovascular diseases. A lot of effort has been put both into academia and into industry to respond to this societal challenge in order to both understand their biology and to find a way to selectively kill these cells. A lot of cytotoxic agents and metallodrugs target DNA as cancer cells divide faster than healthy cells, but severe side effects are observed on patients. The next generation of chemotherapy will be more selective to avoid side effects. Our response to this challenge is to use transition metal catalysis to selectively activate anti-cancer molecules inside cancer cells. Initially, iridium catalysts capable of reducing imines with the metabolic cofactor NADH were developed. Following this, palladium catalysts capable of deprotecting allyl carbamates in a buffered aqueous medium using the glutathione cofactor were developed. We showed that we were able to activate fluorescent molecules selectively inside cancer cells. Our best candidates were stable, cell permeable and non-toxic in addition to remaining active in the cellular medium. Then, with satisfactory catalysts in hand, we moved on to therapeutical applications. In one hand, we attempted to catalytically inhibit enzymes using our catalysts and in the other hand, we tried to gain selectivity by making prodrugs capable of recognizing cancer-specific proteins at the cell surface.
(SC - Sciences) – UCL, 2019
Advisors/Committee Members: UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity, UCL - Faculté des Sciences, Riant, Olivier, Papot, Sébastien, Garcia, Yann, Singleton, Michael, Madder, Annemieke, Frédéric, Raphael.
Subjects/Keywords: Prodrugs; Bioorthogonal chemistry; Palladium; Iridium; Organometallic catalysis
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APA (6th Edition):
Soetens, M. (2019). Development of transition metal catalysts for bioorthogonal reactions. (Thesis). Université Catholique de Louvain. Retrieved from http://hdl.handle.net/2078.1/216769
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):
Soetens, Mathieu. “Development of transition metal catalysts for bioorthogonal reactions.” 2019. Thesis, Université Catholique de Louvain. Accessed March 04, 2021.
http://hdl.handle.net/2078.1/216769.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Soetens, Mathieu. “Development of transition metal catalysts for bioorthogonal reactions.” 2019. Web. 04 Mar 2021.
Vancouver:
Soetens M. Development of transition metal catalysts for bioorthogonal reactions. [Internet] [Thesis]. Université Catholique de Louvain; 2019. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/2078.1/216769.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Soetens M. Development of transition metal catalysts for bioorthogonal reactions. [Thesis]. Université Catholique de Louvain; 2019. Available from: http://hdl.handle.net/2078.1/216769
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Ottawa
25.
Petrov, Ivan.
The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
.
Degree: 2011, University of Ottawa
URL: http://hdl.handle.net/10393/19788
► The regioselectivity in Pd(0)-catalyzed direct arylation of pyrrole, thiophene, and indole can be improved by blocking some of the reactive sites with a chloride group,…
(more)
▼ The regioselectivity in Pd(0)-catalyzed direct arylation of pyrrole, thiophene, and indole can be improved by blocking some of the reactive sites with a chloride group, leading to increased yields of the desired regioisomers. Competition experiments and computational studies show that the blocking group also activates the substrates toward arylation. Due to the activated nature of chlorinated heteroaromatics, rare and sought after regioisomers, such as 3-arylthiophenes, can be obtained under mild conditions in good yields. Chlorine-bearing thiophenes arylated at C3 and C4 have the potential to undergo controlled regioregular polymerization under conditions developed in the field of polythiophene chemistry. Mechanistic studies support the hypothesis that the arylation of the substrates under investigation likely proceeds via the CMD transition state.
Subjects/Keywords: direct arylation;
chlorination;
heteroaromatics;
palladium catalysis
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APA (6th Edition):
Petrov, I. (2011). The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
. (Thesis). University of Ottawa. Retrieved from http://hdl.handle.net/10393/19788
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):
Petrov, Ivan. “The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
.” 2011. Thesis, University of Ottawa. Accessed March 04, 2021.
http://hdl.handle.net/10393/19788.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
MLA Handbook (7th Edition):
Petrov, Ivan. “The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
.” 2011. Web. 04 Mar 2021.
Vancouver:
Petrov I. The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
. [Internet] [Thesis]. University of Ottawa; 2011. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/10393/19788.
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
Council of Science Editors:
Petrov I. The Impact of Chlorine Substituents on the Regioselectivity of Pd(0)-catalyzed Direct Arylation of Heteroaromatics
. [Thesis]. University of Ottawa; 2011. Available from: http://hdl.handle.net/10393/19788
Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation
University of Toronto
26.
Howell, Jennifer K.
Studies in Palladium Catalyzed Carbohalogenation Chemistry.
Degree: 2012, University of Toronto
URL: http://hdl.handle.net/1807/32246
► Since recognizing the significance of reversible oxidative addition of palladium into aryl halides in the synthesis of 2-bromo-indoles, the Lautens group has focused on unusual…
(more)
▼ Since recognizing the significance of reversible oxidative addition of palladium into aryl halides in the synthesis of 2-bromo-indoles, the Lautens group has focused on unusual carbon-halogen reductive eliminations. These efforts led to the discovery of the novel palladium-catalyzed inter- and intramolecular carbohalogenation reaction – the formal addition of an sp2 carbon–iodide bond across an alkene. One current research direction is utilizing a range of aryl halides and pseudohalides as starting materials for carbohalogenation chemistry. This thesis describes complementary research, focusing on the expansion of functional group scope. Carbohalogenation has been developed to synthesize novel products including heteroaromatic compounds and 7-membered rings. Polyunsaturated aryl iodide substrates were investigated with the goal of performing domino carbohalogenation. Ultimately, the successful halogen exchange process was combined with domino carbohalogenation in an efficient halogen-exchange domino reaction. Additionally, preliminary studies on enantioselective carbohalogenation, and functionalization of the neopentyl iodide products are also discussed.
MAST
Advisors/Committee Members: Lautens, Mark, Chemistry.
Subjects/Keywords: catalysis; palladium; domino chemistry; carbohalogenation; 0490
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APA (6th Edition):
Howell, J. K. (2012). Studies in Palladium Catalyzed Carbohalogenation Chemistry. (Masters Thesis). University of Toronto. Retrieved from http://hdl.handle.net/1807/32246
Chicago Manual of Style (16th Edition):
Howell, Jennifer K. “Studies in Palladium Catalyzed Carbohalogenation Chemistry.” 2012. Masters Thesis, University of Toronto. Accessed March 04, 2021.
http://hdl.handle.net/1807/32246.
MLA Handbook (7th Edition):
Howell, Jennifer K. “Studies in Palladium Catalyzed Carbohalogenation Chemistry.” 2012. Web. 04 Mar 2021.
Vancouver:
Howell JK. Studies in Palladium Catalyzed Carbohalogenation Chemistry. [Internet] [Masters thesis]. University of Toronto; 2012. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/1807/32246.
Council of Science Editors:
Howell JK. Studies in Palladium Catalyzed Carbohalogenation Chemistry. [Masters Thesis]. University of Toronto; 2012. Available from: http://hdl.handle.net/1807/32246
Boston College
27.
Edelstein, Emma Kate.
Enantioselective synthesis and stereospecific
transformations of organoboronic esters.
Degree: PhD, Chemistry, 2018, Boston College
URL: http://dlib.bc.edu/islandora/object/bc-ir:108038
► This dissertation details the development of several enantioselective or stereospecific transformations involving organoboronic esters. Chapter one will introduce electrophile-induced boronate rearrangements which underpins much of…
(more)
▼ This dissertation details the development of several
enantioselective or stereospecific transformations involving
organoboronic esters. Chapter one will introduce
electrophile-induced boronate rearrangements which underpins much
of the reactivity that will be discussed in subsequent chapters. In
chapter two the conjunctive cross-coupling reaction is presented.
Its development and application to the synthesis of non-racemic
boronic esters, along with its application to the synthesis of
enantioenriched allylic boronic esters, will be discussed. In
chapter three the cross-coupling of geminal bis(boronic) esters is
introduced and the development of a method to employ them in
cross-coupling with alkenyl bromides, affording enantioenriched
substituted allylic boronic esters is outlined. In chapter four we
highlight the utility of allylic boronic esters, and detail the
development of a cross-coupling reaction that involves the use of
these substrates and halide electrophiles to furnish
enantiomerically enriched products containing all carbon quaternary
stereocenters. Finally, in chapter five we describe the development
of a metalfree amination reaction of organoboron compounds, which
is able to deliver otherwise difficult-to-access enantiomerically
enriched α-tertiary amines.
Advisors/Committee Members: James P. Morken (Thesis advisor).
Subjects/Keywords: Boron; Catalysis; Cross-Coupling; Enantioselective; Palladium; Stereospecific
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APA ·
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MLA ·
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Export
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APA (6th Edition):
Edelstein, E. K. (2018). Enantioselective synthesis and stereospecific
transformations of organoboronic esters. (Doctoral Dissertation). Boston College. Retrieved from http://dlib.bc.edu/islandora/object/bc-ir:108038
Chicago Manual of Style (16th Edition):
Edelstein, Emma Kate. “Enantioselective synthesis and stereospecific
transformations of organoboronic esters.” 2018. Doctoral Dissertation, Boston College. Accessed March 04, 2021.
http://dlib.bc.edu/islandora/object/bc-ir:108038.
MLA Handbook (7th Edition):
Edelstein, Emma Kate. “Enantioselective synthesis and stereospecific
transformations of organoboronic esters.” 2018. Web. 04 Mar 2021.
Vancouver:
Edelstein EK. Enantioselective synthesis and stereospecific
transformations of organoboronic esters. [Internet] [Doctoral dissertation]. Boston College; 2018. [cited 2021 Mar 04].
Available from: http://dlib.bc.edu/islandora/object/bc-ir:108038.
Council of Science Editors:
Edelstein EK. Enantioselective synthesis and stereospecific
transformations of organoboronic esters. [Doctoral Dissertation]. Boston College; 2018. Available from: http://dlib.bc.edu/islandora/object/bc-ir:108038
Boston College
28.
Szymaniak, Adam Anthony.
Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions.
Degree: PhD, Chemistry, 2018, Boston College
URL: http://dlib.bc.edu/islandora/object/bc-ir:108119
► This dissertation will describe the development of three transition metal-catalyzed syntheses of nonracemic organoboronates. The first chapter explains the development of a palladium-catalyzed enantiotopic-group-selective cross-coupling…
(more)
▼ This dissertation will describe the development of
three transition metal-catalyzed syntheses of nonracemic
organoboronates. The first chapter explains the development of a
palladium-catalyzed enantiotopic-group-selective cross-coupling of
geminal bis(boronates) with alkenyl electrophiles. This process
enables the synthesis of highly valuable nonracemic disubstituted
allylic boronates. Chapter two describes a
palladium-induced
1,2-metallate rearrangement of vinylboron “ate” complexes. The
newly developed process incorporates an alternative route for the
transmetallation step of Suzuki-Miyaura cross-couplings. Lastly, an
enantioselective platinum-catalyzed hydrosilylation of alkenyl
boronates is disclosed. This reaction enables the synthesis of
nonracemic geminal silylboronates for the divergent synthesis of
functionalized
Advisors/Committee Members: James P. Morken (Thesis advisor).
Subjects/Keywords: catalysis; enantioselective; nonracemic; organoboronates; palladium; platinum
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APA ·
Chicago ·
MLA ·
Vancouver ·
CSE |
Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Szymaniak, A. A. (2018). Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions. (Doctoral Dissertation). Boston College. Retrieved from http://dlib.bc.edu/islandora/object/bc-ir:108119
Chicago Manual of Style (16th Edition):
Szymaniak, Adam Anthony. “Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions.” 2018. Doctoral Dissertation, Boston College. Accessed March 04, 2021.
http://dlib.bc.edu/islandora/object/bc-ir:108119.
MLA Handbook (7th Edition):
Szymaniak, Adam Anthony. “Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions.” 2018. Web. 04 Mar 2021.
Vancouver:
Szymaniak AA. Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions. [Internet] [Doctoral dissertation]. Boston College; 2018. [cited 2021 Mar 04].
Available from: http://dlib.bc.edu/islandora/object/bc-ir:108119.
Council of Science Editors:
Szymaniak AA. Nonracemic Organoboronates by Transition Metal-Catalyzed C-C
and C-Si Bond Forming Reactions. [Doctoral Dissertation]. Boston College; 2018. Available from: http://dlib.bc.edu/islandora/object/bc-ir:108119
University of Colorado
29.
Schoenbaum, Carolyn.
Controlling Catalyst Active Sites Using Self-Assembled Monolayers.
Degree: PhD, Chemical & Biochemical Engineering, 2014, University of Colorado
URL: https://scholar.colorado.edu/chbe_gradetds/63
► Elucidating the site requirements for reactions over heterogeneous catalysts can be challenging since, unlike their homogenous counterparts, the surfaces of these materials are comprised…
(more)
▼ Elucidating the site requirements for reactions over heterogeneous catalysts can be challenging since, unlike their homogenous counterparts, the surfaces of these materials are comprised of a variety of diverse features where reactions can occur. Because there is strong evidence suggesting that reactions will occur at a specific type (or group) of active site(s), significant effort has been put forth in the field to try to determine the site requirements for particular reactions. Here, we report a new approach for controlling the availability of specific active sites on supported Pd/Al
2O
3 catalysts using alkanethiolate self-assembled monolayers (SAMs). SAMs form consistent and ordered structures on metal surfaces; these features were exploited to form monolayers that preferentially block or expose specific types of sites on catalyst particles.
The structure of the tail moiety played an important role in the overall organization of the resulting monolayer and was tuned to control the types of active sites that were exposed on metal particle surfaces. Infrared spectroscopy using CO as a probe molecule was used to characterize site availability on the catalysts. A monolayer formed from a bulky caged molecule like 1-adamanetanethiol (AT) restricted the availability of contiguous active sites on particle terraces with respect to the uncoated catalyst. Increasing the density of the monolayer using a linear alkanethiol like 1-octadecanethiol (C18) further restricted adsorption on terraces. For both of these monolayers, adsorption at particle edges and steps was nearly unaffected but could be blocked by forming a high coverage monolayer from 1,2-benzene dithiol (BDT).
The relationship between monolayer spacing and reactivity dramatically depended on the structure of the reactant, even for small species. For example, employing a C18 monolayer reduced the rate of epoxybutane hydrogenation by nearly 3 orders of magnitude with respect to the unmodified catalyst, whereas hydrogenation of propionaldehyde was only reduced by a single order of magnitude. These results suggested 1) that site requirements for conversion of these two species were substantially different and 2) this modification approach could potentially be utilized to direct selectivity of more complex reactants where competing reaction pathways have different site requirements.
To demonstrate the feasibility of the latter hypothesis, this approach was utilized for the hydrogenation of furfural. On
palladium catalysts, furfural tends to decarbonylate to produce furan and carbon monoxide. A competing process involves hydrogenation of the aldehyde to produce furfuryl alcohol and subsequent hydrodeoxygenation producing methylfuran. Site requirements for each pathway were investigated by comparing reactivity on uncoated, C18-coated and BDT-coated catalysts. Comparison between reaction rates and site availability suggested that decarbonylation occurred primarily on terrace sites while hydrodeoxygenation occurred on particle…
Advisors/Committee Members: J. Will Medlin, Daniel K. Schwartz, Charles B. Musgrave, Garry Rumbles, Joel L. Kaar.
Subjects/Keywords: catalysis; hydrogenation; palladium; reactivity; Chemical Engineering
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APA (6th Edition):
Schoenbaum, C. (2014). Controlling Catalyst Active Sites Using Self-Assembled Monolayers. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chbe_gradetds/63
Chicago Manual of Style (16th Edition):
Schoenbaum, Carolyn. “Controlling Catalyst Active Sites Using Self-Assembled Monolayers.” 2014. Doctoral Dissertation, University of Colorado. Accessed March 04, 2021.
https://scholar.colorado.edu/chbe_gradetds/63.
MLA Handbook (7th Edition):
Schoenbaum, Carolyn. “Controlling Catalyst Active Sites Using Self-Assembled Monolayers.” 2014. Web. 04 Mar 2021.
Vancouver:
Schoenbaum C. Controlling Catalyst Active Sites Using Self-Assembled Monolayers. [Internet] [Doctoral dissertation]. University of Colorado; 2014. [cited 2021 Mar 04].
Available from: https://scholar.colorado.edu/chbe_gradetds/63.
Council of Science Editors:
Schoenbaum C. Controlling Catalyst Active Sites Using Self-Assembled Monolayers. [Doctoral Dissertation]. University of Colorado; 2014. Available from: https://scholar.colorado.edu/chbe_gradetds/63
University of Minnesota
30.
Eastwood, Matthew.
Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis.
Degree: PhD, Chemistry, 2019, University of Minnesota
URL: http://hdl.handle.net/11299/216889
► Chapter 1. A survey of the literature to date on the palladium-catalyzed cyanoamidation reaction, both in terms of synthesis and mechanism. Details of work expanding…
(more)
▼ Chapter 1. A survey of the literature to date on the palladium-catalyzed cyanoamidation reaction, both in terms of synthesis and mechanism. Details of work expanding the substrate scope of diastereoselective alkene cyanoamidation, as well as studies toward the removal of the chiral directing group, which necessitated development of a method for chemoselective reduction of hindered lactams in the presence of nitriles. Chapter 2. A review of the literature regarding the synthesis of asymmetric Aspidosperma alkaloids quebrachamine and eburnamonine. Approaches to scalemic material by a wide variety of routes. Chapter 3. A discussion of work towards an enantioselective cyanoamidation of a highly functionalized aliphatic-tethered alkene towards the synthesis of Aspidosperma alkaloids is presented. Efforts toward the functionalization of cyanoamidation products towards quebrachamine, including attempts at forming the alkaloid’s nine-membered ring and the application of diastereoselective cyanoamidation, are discussed. A successful total synthesis of (+)-eburnamonine in four steps from the scalemic cyanoamidation product. Chapter 4. A review of the literature published to date on the synthesis of madangamine alkaloids, including approaches to the diazatricyclic core, macrocyclic rings, and completed total syntheses of various members of the madangamine family. Chapter 5. A discussion of the variety of approaches undertaken towards the synthesis of a di(cyanoformamide) thought to be a viable substrate for a cyanoamidation-based C–C bond activation cascade for making the madangamine core. Details of the development of said cascade reaction and successful synthesis of a madangamine core derivative.
Subjects/Keywords: Cyanoamidation; Eburnamonine; Madangamine; Palladium catalysis; Quebrachamine
Record Details
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Record Details
Similar Records
Cite
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❌
APA ·
Chicago ·
MLA ·
Vancouver ·
CSE |
Export
to Zotero / EndNote / Reference
Manager
APA (6th Edition):
Eastwood, M. (2019). Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis. (Doctoral Dissertation). University of Minnesota. Retrieved from http://hdl.handle.net/11299/216889
Chicago Manual of Style (16th Edition):
Eastwood, Matthew. “Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis.” 2019. Doctoral Dissertation, University of Minnesota. Accessed March 04, 2021.
http://hdl.handle.net/11299/216889.
MLA Handbook (7th Edition):
Eastwood, Matthew. “Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis.” 2019. Web. 04 Mar 2021.
Vancouver:
Eastwood M. Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis. [Internet] [Doctoral dissertation]. University of Minnesota; 2019. [cited 2021 Mar 04].
Available from: http://hdl.handle.net/11299/216889.
Council of Science Editors:
Eastwood M. Development of Stereoselective Cyanoamidation Reactions and Their Application to Natural Product Total Synthesis. [Doctoral Dissertation]. University of Minnesota; 2019. Available from: http://hdl.handle.net/11299/216889
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