Photoinduced Low‐Valent Zirconium Catalysis for Cross‐Electrophile Coupling of Ethers

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 23, 2024

Abstract Accessing versatile C( sp3 )−C( ) bond through the cross‐electrophile coupling of two distinct etheric C−O bonds is crucial in organic synthesis but remains barely explored. Herein, we report an innovative photoinduced low‐valent zirconocene catalysis enabling reductive ethers with high activity and cross‐selectivity. Mechanistic investigation suggests that photoexcitation facilitates )−O scission benzylic ethers, leading to radicals intermediate via a single‐electron reduction pathway. The subsequent recombination this radical Zr center followed by carbomagnesiation generates Grignard reagents for downstream aliphatic S N 2‐like mechanism. In application, wide range readily situ derived from aldehydes ketones becomes feasible functional group compatibility as well excellent

Language: Английский

Photoinduced Low‐Valent Zirconium Catalysis for Cross‐Electrophile Coupling of Ethers

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 23, 2024

Abstract Accessing versatile C( sp3 )−C( ) bond through the cross‐electrophile coupling of two distinct etheric C−O bonds is crucial in organic synthesis but remains barely explored. Herein, we report an innovative photoinduced low‐valent zirconocene catalysis enabling reductive ethers with high activity and cross‐selectivity. Mechanistic investigation suggests that photoexcitation facilitates )−O scission benzylic ethers, leading to radicals intermediate via a single‐electron reduction pathway. The subsequent recombination this radical Zr center followed by carbomagnesiation generates Grignard reagents for downstream aliphatic S N 2‐like mechanism. In application, wide range readily situ derived from aldehydes ketones becomes feasible functional group compatibility as well excellent

Language: Английский