Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3989 - 3997

Published: Feb. 22, 2022

Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general modular platform to access α-aryl phosphorus compounds via Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates aryl iodides. This dual catalytic regime exhibited high efficiency good functional group compacity. A wide variety of substrates bearing diverse set groups could be converted into phosphates excellent yields enantioselectivities. The utility the method was also demonstrated by development new phosphine ligand synthesis enzyme inhibitor derivatives. detailed mechanistic studies supported radical chain process revealed unique distinction compared with traditional cross-coupling.

Language: Английский

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Alkene Hydrobenzylation by a Single Catalyst That Mediates Iterative Outer-Sphere Steps

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2351 - 2357

Published: Jan. 17, 2024

Cross-coupling catalysts typically react and unite functionally distinct partners via sequential inner-sphere elementary steps: coordination, migratory insertion, reductive elimination, etc. Here, we report a single catalyst that cross-couples styrenes benzyl bromides iterative outer-sphere metal–ligand-carbon interactions. Each partner forms stabilized radical intermediate, yet heterocoupled products predominate. The system is redox-neutral and, thus, avoids exogenous oxidants, resulting in simple scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged heterodibenzyl (1,2-diarylethane) motif challenging quaternary carbon variants.

Language: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

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BI-OAc-Accelerated C3–H Alkylation of Quinoxalin-2(1H)-ones under Visible-Light Irradiation

Organic Letters, Journal Year: 2020, Volume and Issue: 22(15), P. 5984 - 5989

Published: July 24, 2020

An efficient, photoredox-catalyst-free radical alkylation of quinoxalin-2(1H)-ones has been described. This reaction utilizes 4-alkyl-1,4-dihydropyridines (R-DHPs) as alkyl precursors and acetoxybenziodoxole (BI-OAc) an electron acceptor to undergo single-electron transfer with photoexcited R-DHPs. The benign conditions allow for good compatibility in the scope both synthetic value protocol was also demonstrated by successful functionalization natural products drug-based complex molecules

Language: Английский

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Advances in asymmetric visible-light photocatalysis, 2015–2019

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(38), P. 8673 - 8689

Published: Jan. 1, 2019

Asymmetric visible-light photocatalysis has recently drawn considerable attention of the scientific community owing to its unique activation modes and significance for enantioselective green synthesis.

Language: Английский

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