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Transition-metal-catalyzed and transition-metal-free activation of amides and esters by highly selective N–C/O–C cleavage
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Li, Guangchen. Transition-metal-catalyzed and transition-metal-free activation of amides and esters by highly selective N–C/O–C cleavage. Retrieved from https://doi.org/doi:10.7282/t3-v4ft-p785

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TitleTransition-metal-catalyzed and transition-metal-free activation of amides and esters by highly selective N–C/O–C cleavage
NameLi, Guangchen (author); Szostak, Michal (chair); Jaekle, Frieder (member); Chen, Hao (member); He, Huixin (member); Rutgers University; Graduate School - Newark
Date Created2022
Other Date2022-10 (degree)
SubjectOrganic chemistry, Amide, Cross-coupling, C–N/C–O bonds activation, Ester, Transition-metal-catalyzed, Transition-metal-free
Extent333 pages : illustrations
DescriptionAmide and ester bonds are among the most important functional groups in chemistry and biology. It is noteworthy that the amide bond formation represents the most common reaction performed by medicinal chemists, with more than 75% of prospective drug candidates containing amide bond. The development of new methods for activation of acyl C–N/C–O bonds of amides and esters has historically represented an attractive challenge in organic synthesis. However, the classical resonance nN → π*C=O and nO → π*C=O in amides and esters results in a high stability of common amides and esters. This dissertation presents studies on achieving activation of amide and ester bonds via ground-state-destabilization strategy to facilitate selective N–C(O) and O–C(O) bond activation for transition-metal-catalyzed acyl cross-coupling and transition-metal-free reactions via tetrahedral intermediates. The first part of this thesis will detail our studies on Pd–NHC-catalyzed cross-coupling reactions of esters and amides via acyl-metal intermediates, including 1) the development of Pd–NHC-catalyzed water-assisted Suzuki–Miyaura cross-coupling of aryl esters; 2) the development of Pd–NHC-catalyzed Suzuki–Miyaura cross-coupling of amides using industrially-relevant, sterically-hindered IPr* NHC ligand; 3) the development of Pd–NHC-catalyzed acyl Buchwald–Hartwig cross-coupling of amides with functionalized anilines. The second part of this thesis will discuss the development of highly chemoselective transition-metal-free methods for transforamtions of amides and esters via tetrahedral intermediates, including 1) the development of transition-metal-free esterification of amides; 2) the development of transition-metal-free transamidation of amides and amidation of esters at room temperature; 3) the development of acylation of functionalized Grignard reagents with amides; 4) the development of chemoselective transamidation of thioamides by transition-metal-free N–C(S) transacylation. The common feature of all processes described in this Thesis is selective cleavage of amide and ester N–C(O)/O–C(O) bonds with exquisite chemoselectivity by complementary acyl-metal and nucleophilic addition pathways.
NotePh.D.
NoteIncludes bibliographical references
Genretheses
Persistent URLhttps://doi.org/doi:10.7282/t3-v4ft-p785
LanguageEnglish
CollectionGraduate School - Newark Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.
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