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You searched for subject:(Amides Electric properties). Showing records 1 – 2 of 2 total matches.

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Rutgers University

1. Meng, Guangrong, 1987-. Cross-coupling of amides by N-C bond activation.

Degree: PhD, Chemistry, 2019, Rutgers University

The amide bond is one the most important functional motifs in chemistry and biology. However, despite the central role of amides as ubiquitous pharmacophores in medicinal chemistry, but also as bench-stable intermediates in organic synthesis, transition-metal- catalyzed transformations of amides by N-C bond activation have been unexplored. The major reason is that high activation energy is required for the N-C(O) bond scission due to nN→*πC=O conjugation (amide bond resonance of 15-20 kcal/mol in planar amides, ca. 40% double bond character). In 2015, we introduced a new generic mode of activation of amide bonds by geometric distortion, whereby metal insertion into an inert amide bond can proceed only if the classic Pauling's amide bond resonance has been disrupted. With this new concept put forward, we successfully developed several new types of twisted amides and metal-catalyzed transformations during my Ph.D. research. The focus of this thesis is on three parts: (1) the use of amides as acyl electrophiles in metal-catalyzed Suzuki cross-coupling reactions; (2) the use of amides as aryl electrophiles in metal-catalyzed cross-coupling reactions, including palladium-catalyzed Heck reaction and rhodium-catalyzed C-H bond functionalization; (3) the development of new type of amides as acyl electrophiles with the use of new Pd-NHC catalyst systems. These studies have demonstrated the potential of amides as acyl- and aryl-electrophiles in catalytic cross-coupling chemistry by activation of the typically inert amide N-C(O) bond.

Advisors/Committee Members: Szostak, Michal (chair), He, Huixin (internal member), Sheridan, John (internal member), Lakshman, Mahesh (outside member).

Subjects/Keywords: Twisted amides; Amides  – Electric properties

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Meng, Guangrong, 1. (2019). Cross-coupling of amides by N-C bond activation. (Doctoral Dissertation). Rutgers University. Retrieved from https://rucore.libraries.rutgers.edu/rutgers-lib/61660/

Chicago Manual of Style (16th Edition):

Meng, Guangrong, 1987-. “Cross-coupling of amides by N-C bond activation.” 2019. Doctoral Dissertation, Rutgers University. Accessed January 21, 2020. https://rucore.libraries.rutgers.edu/rutgers-lib/61660/.

MLA Handbook (7th Edition):

Meng, Guangrong, 1987-. “Cross-coupling of amides by N-C bond activation.” 2019. Web. 21 Jan 2020.

Vancouver:

Meng, Guangrong 1. Cross-coupling of amides by N-C bond activation. [Internet] [Doctoral dissertation]. Rutgers University; 2019. [cited 2020 Jan 21]. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/61660/.

Council of Science Editors:

Meng, Guangrong 1. Cross-coupling of amides by N-C bond activation. [Doctoral Dissertation]. Rutgers University; 2019. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/61660/


Rutgers University

2. Shi, Shicheng, 1988-. Development of new methods for activation of inert N-C bonds.

Degree: PhD, Chemistry, 2019, Rutgers University

The amide bond is one of the most important functional groups in chemistry and biology. It would be appealing to use amides as N-C(O) electrophiles in transition-metal-catalyzed cross-coupling reactions, however, the high activation energy required for N-C(O) scission, a consequence of amidic resonance (approximately 40% double bond character in planar amides, 15-20 kcal/mol barrier to rotation), makes selective metal insertion into the N-C(O) bond a classic problem in catalysis. In 2015, our group introduced a new mode for amide bond activation enabled through ground-state-destabilization. Based on this concept, we have successfully developed N-acyl-glutarimide amides as highly effective amide-based electrophiles, in which the amide bond exhibits nearly perpendicular twist (T = 87.8º). This thesis describes our studies on: 1) the development of novel transition-metal-catalyzed transformations of amides by N-C(O) activation; 2) the development of new amide precursors for cross-coupling reactions; 3) the development of new, general catalytic systems for acyl-cross-coupling reactions. Specifically, the thesis addresses: 1) the development of novel decarbonylative cross-coupling reactions using amides as aryl equivalents, including Ni-catalyzed decarbonylative Suzuki cross-coupling, Pd-catalyzed decarbonylative cyanation, and Pd-catalyzed decarbonylative borylation; 2) the development of a general catalytic system for acyl Negishi cross-coupling reactions of N-acyl-glutarimides, N,N-di-Boc2 amides and N-acyl-succinimides; 3) the development of Pd-NHC catalytic systems for acyl Suzuki cross-coupling of esters, acyl Buchwald-Hartwig cross-coupling of amides and esters, and acyl Suzuki cross-coupling of triflamides.

Advisors/Committee Members: Szostak, Michal (chair), Jordan, Frank (internal member), Lalancette, Roger (internal member), Williams, Lawrence (outside member).

Subjects/Keywords: Amide bond activation; Amides  – Electric properties

Record DetailsSimilar RecordsGoogle PlusoneFacebookTwitterCiteULikeMendeleyreddit

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Shi, Shicheng, 1. (2019). Development of new methods for activation of inert N-C bonds. (Doctoral Dissertation). Rutgers University. Retrieved from https://rucore.libraries.rutgers.edu/rutgers-lib/61666/

Chicago Manual of Style (16th Edition):

Shi, Shicheng, 1988-. “Development of new methods for activation of inert N-C bonds.” 2019. Doctoral Dissertation, Rutgers University. Accessed January 21, 2020. https://rucore.libraries.rutgers.edu/rutgers-lib/61666/.

MLA Handbook (7th Edition):

Shi, Shicheng, 1988-. “Development of new methods for activation of inert N-C bonds.” 2019. Web. 21 Jan 2020.

Vancouver:

Shi, Shicheng 1. Development of new methods for activation of inert N-C bonds. [Internet] [Doctoral dissertation]. Rutgers University; 2019. [cited 2020 Jan 21]. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/61666/.

Council of Science Editors:

Shi, Shicheng 1. Development of new methods for activation of inert N-C bonds. [Doctoral Dissertation]. Rutgers University; 2019. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/61666/

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