Decarboxylative Negishi Coupling of Redox‐Active Aliphatic Esters by Cobalt Catalysis

Liu, Xu‐Ge; Zhou, Chu‐Jun; Lin, E; Han, Xiang‐Lei; Zhang, Shang‐Shi; Li, Qingjiang; Wang, Honggen

doi:10.1002/anie.201806799

Cited by 83 publications

(48 citation statements)

References 95 publications

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“…For this purpose, one feasible way is to activate the carboxylic acids and alkyl primary amines to the corresponding redox-active esters (RAE) and Katritzky's N-alkylpyridinium salts, respectively 16,17 . Previous studies demonstrated that both RAE [18][19][20][21][22][23][24][25][26][27][28] and Katritzky's salts [29][30][31][32][33][34][35][36][37] are predisposed to accept an electron from low-valent transition metals or organic Lewis bases under photocatalytic reaction conditions, thereby acting as precursors to the corresponding alkyl radicals (Fig. 1b) [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] .…”

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confidence: 99%

Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

et al. 2020

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Alkyl carboxylic acids as well as primary amines are ubiquitous in all facets of biological science, pharmaceutical science, chemical science and materials science. By chemical conversion to redox-active esters (RAE) and Katritzky’s N-alkylpyridinium salts, respectively, alkyl carboxylic acids and primary amines serve as ideal starting materials to forge new connections. In this work, a Mn-mediated reductive decarboxylative/deaminative functionalization of activated aliphatic acids and primary amines is disclosed. A series of C-X (X = S, Se, Te, H, P) and C-C bonds are efficiently constructed under simple and mild reaction conditions. The protocol is applicable to the late-stage modification of some structurally complex natural products or drugs. Preliminary mechanistic studies suggest the involvement of radicals in the reaction pathway.

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Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

et al. 2020

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“…Furthermore, decarboxylative fragmentation of redox active esters (RAEs) enables the generation of alkyl radicals under photoredox conditions using Ir, Ru, and other photocatalysts . Meanwhile, transition metals such as Ni, Fe, Cu, Co, Cr, and other metal species have also been used to reduce RAEs via thermal single‐electron transfer (SET) to form alkyl radicals. Through similar mechanisms, oxalate derivatives can produce tertiary radicals through Ir‐, Ru‐catalyzed photoredox conditions or Zn metal and Ni with ligands .…”

Section: Figurementioning

confidence: 99%

Catalyst‐Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro‐Induced Radical Formation

Chen

Luo

Peng

et al. 2020

Chemistry A European J

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Electro‐induced reduction of redox active esters and N‐phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron‐poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst‐free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.

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“…quaternary stereogenic centers. Furthermore, the NHPIbased redox-active esters can also accept electrons from simple metal catalysts, such as cobalt, 41 copper, 42,43 iron, 44 and nickel, [45][46][47][48][49][50] through thermal SET events. 51,52 Inspired by the work of the Okada and Oda group, in 2016 the König group reported a metal-free method for the decarboxylative alkylation of biomass-derived carboxylic acids (Scheme 2).…”

Section: Syn Thesismentioning

confidence: 99%

Recent Advances in Photoredox Catalysis Enabled Functionalization of α-Amino Acids and Peptides: Concepts, Strategies and Mechanisms

et al. 2019

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The selective modification of α-amino acids and peptides constitutes a pivotal arena for accessing new peptide-based materials and therapeutics. In recent years, visible light photoredox catalysis has appeared as a powerful platform for the activation of small molecules via single-electron transfer events, allowing previously inaccessible reaction pathways to be explored. This review outlines the recent advances, mechanistic underpinnings, and opportunities of applying photoredox catalysis to the expansion of the synthetic repertoire for the modification of specific amino acid residues.1 Introduction2 Visible-Light-Mediated Functionalization of α-Amino Acids2.1 Decarboxylative Functionalization Involving Redox-Active Esters2.2 Direct Decarboxylative Coupling Strategies2.3 Hypervalent Iodine Reagents2.4 Dual Photoredox and Transition-Metal Catalysis2.5 Amination and Deamination Strategies3 Photoinduced Peptide Diversification3.1 Gese-Type Bioconjugation Methods3.2 Peptide Macrocyclization through Photoredox Catalysis3.3 Biomolecule Conjugation through Arylation3.4 C–H Functionalization Manifolds4 Conclusions and Outlook

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Decarboxylative Negishi Coupling of Redox‐Active Aliphatic Esters by Cobalt Catalysis

Cited by 83 publications

References 95 publications

Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

Catalyst‐Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro‐Induced Radical Formation

Recent Advances in Photoredox Catalysis Enabled Functionalization of α-Amino Acids and Peptides: Concepts, Strategies and Mechanisms

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