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Visible‐Light Photoredox‐Catalyzed Remote Difunctionalizing Carboxylation of Unactivated Alkenes with CO 2
Author(s) -
Song Lei,
Fu DongMin,
Chen Liang,
Jiang YuanXu,
Ye JianHeng,
Zhu Lei,
Lan Yu,
Fu Qiang,
Yu DaGang
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202008630
Subject(s) - chemistry , nucleophile , alkene , radical , catalysis , carbanion , photochemistry , functional group , carboxylation , substrate (aquarium) , photoredox catalysis , combinatorial chemistry , hydrogen atom , formate , visible spectrum , organic chemistry , group (periodic table) , photocatalysis , materials science , oceanography , geology , polymer , optoelectronics
Remote difunctionalization of unactivated alkenes is challenging but a highly attractive tactic to install two functional groups across long distances. Reported herein is the first remote difunctionalization of alkenes with CO 2 . This visible‐light photoredox catalysis strategy provides a facile method to synthesize a series of carboxylic acids bearing valuable fluorine‐ or phosphorus‐containing functional groups. Moreover, this versatile protocol shows mild reaction conditions, broad substrate scope, and good functional‐group tolerance. Based on DFT calculations, a radical adds to an unactivated alkene to smoothly form a new carbon radical, followed by a 1,5‐hydrogen atom‐transfer process, the rate‐limiting step, generating a more stable benzylic radical. The reduction of the benzylic radicals by an Ir II species generates the corresponding benzylic carbanions as the key intermediates, which further undergo nucleophilic attack with CO 2 to generate carboxylates.