Dual Photoredox and Copper Catalysis: Enantioselective 1,2-Amidocyanation of 1,3-Dienes DOI

Dan Forster,

Wei‐Si Guo,

Qian Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7523 - 7528

Published: May 19, 2023

Dual photoredox–transition-metal catalysis has emerged as a powerful tool for the development of chemical transformations. However, its application in selective difunctionalization 1,3-dienes remains essentially unexploited. By synergistic action photoredox and copper catalysts, we report herein an enantioselective 1,2-amidocyanation 1,3-dienes. Visible-light irradiation chloroform solution conjugated dienes, N-Boc-amidopyridinium salts, TMSCN presence catalytic amount fac-Ir(ppy)3, Cu(OTf)2·xH2O, chiral Box ligand affords three-component adducts good to high yields with regio- enantioselectivities. A L*CuCN complex, fully characterized spectroscopically confirmed by X-ray crystallographic analysis, is able catalyze transformation, therefore supporting inner-sphere cyanide transfer pathway.

Language: Английский

Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling DOI
Jun Chen, Yujie Liang,

Peng‐Zi Wang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13382 - 13392

Published: Aug. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Language: Английский

Citations

156
Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention DOI

Fu‐Dong Lu,

Jun Chen, Xuan‐Feng Jiang

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(22), P. 12808 - 12827

Published: Jan. 1, 2021

Transition metal-catalysed asymmetric coupling has been established as a robust tool for constructing complex organic molecules. Although this area extensively studied, the development of efficient protocols to construct stereogenic centres with excellent regio- and enantioselectivities is highly desirable remains challenging. Asymmetric transition metal catalysis light intervention provides practical alternative strategy current methods considerably expands synthetic utility result abundant feedstocks mild conditions. This tutorial review comprehensively summarizes recent advances in transition-metal-catalysed reactions intervention; particular, concise analysis substrate scope mechanistic scenarios governing stereocontrol discussed.

Language: Английский

Citations

141
Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Coupling of 1,3‐Dienes: An Alternative to Kharasch–Sosnovsky Reaction DOI

Peng‐Zi Wang,

Xue Wu, Ying Cheng

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(42), P. 22956 - 22962

Published: Aug. 18, 2021

Abstract Kharasch–Sosnovsky reaction is one of the most powerful methods for allylic oxidation alkenes. However, inherent radical mechanism and use peroxides as both oxidants oxygen nucleophiles render dearth universal catalytic systems highly enantioselective variants limited scope. Herein, an alternative to asymmetric that utilized a chiral copper catalyst purple‐LED irradiation enable three‐component coupling 1,3‐dienes, oxime esters, carboxylic acids reported. This protocol features mild conditions, remarkable scope functional group tolerance evidenced by >80 examples utility in late‐stage modification pharmaceuticals natural products. Detailed mechanistic studies provide evidences radical‐based pathway.

Language: Английский

Citations

121
Copper-photocatalyzed ATRA reactions: concepts, applications, and opportunities DOI
Sebastian Engl, Oliver Reiser

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(13), P. 5287 - 5299

Published: Jan. 1, 2022

This review summarizes the different applications and underlying concepts that are applied for Cu( i )- or ii )-photocatalyzed difunctionalizations of alkenes.

Language: Английский

Citations

105
Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides DOI
Xuan‐Feng Jiang, Hao Jiang, Qian Yang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8347 - 8354

Published: April 28, 2022

Grignard addition is one of the most important methods used for syntheses alcohol compounds and has been known over a hundred years. However, research on asymmetric catalysis relies use organometallic nucleophiles. Here, we report first visible-light-induced cobalt-catalyzed reductive Grignard-type synthesizing chiral benzyl alcohols (>50 examples, up to 99% yield, ee). This methodology advantages mild reaction conditions, good functionality tolerance, excellent enantiocontrol, avoidance mass metal wastes, precious catalysts. Kinetic realization studies suggested that migratory insertion an aryl cobalt species into aldehyde was rate-determining step reaction.

Language: Английский

Citations

94
Recent advances in radical-mediated transformations of 1,3-dienes DOI

Peng‐Zi Wang,

Wen‐Jing Xiao, Jia‐Rong Chen

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2022, Volume and Issue: 43(3), P. 548 - 557

Published: Feb. 2, 2022

Language: Английский

Citations

83
Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality DOI
Hao Jiang,

Xiang‐Kui He,

Xuan‐Feng Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6944 - 6952

Published: March 15, 2023

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.

Language: Английский

Citations

82
Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction DOI
Dong Liang, Jia‐Rong Chen, Liping Tan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6040 - 6049

Published: March 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Language: Английский

Citations

78
Photoinduced copper-catalyzed enantioselective coupling reactions DOI
Liangliang Song, Lingchao Cai, Lei Gong

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(7), P. 2358 - 2376

Published: Jan. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Language: Английский

Citations

69
Dynamic Kinetic Reductive Conjugate Addition for Construction of Axial Chirality Enabled by Synergistic Photoredox/Cobalt Catalysis DOI
Wei Xiong, Xuan‐Feng Jiang, Wencheng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7983 - 7991

Published: March 28, 2023

Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and widely used to synthesize natural products drugs. However, asymmetric catalysis studies have mainly focused on stereogenic centers arising from conjugate alkenes. Here, we report first photoinduced cobalt-catalyzed dynamic kinetic reductive reaction that enables formation of heterobiaryls with axial chirality (45 examples, up 91% yield 97% ee). This method features mild conditions, good functional-group tolerance, excellent enantiomeric control. Significantly, large amounts metal waste precious catalysts can be avoided under these conditions. Migration chiral arylcobalt species into alkene might rate-determining step based studies.

Language: Английский

Citations

64