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Visible‐Light‐Driven Palladium‐Catalyzed Radical Alkylation of C−H Bonds with Unactivated Alkyl Bromides
Author(s) -
Zhou WenJun,
Cao GuangMei,
Shen Guo,
Zhu XingYong,
Gui YongYuan,
Ye JianHeng,
Sun Liang,
Liao LiLi,
Li Jing,
Yu DaGang
Publication year - 2017
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.201704513
Subject(s) - chemistry , alkyl , palladium , catalysis , aryl , alkylation , radical , photochemistry , photoredox catalysis , intermolecular force , functional group , photocatalysis , medicinal chemistry , organic chemistry , molecule , polymer
Reported herein is a novel visible‐light photoredox system with Pd(PPh 3 ) 4 as the sole catalyst for the realization of the first direct cross‐coupling of C(sp 3 )−H bonds in N‐aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover, intra‐ and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions. A variety of tertiary, secondary, and primary alkyl bromides undergo reaction to generate C(sp 3 )−C(sp 3 ) and C(sp 2 )−C(sp 3 ) bonds in moderate to excellent yields. These redox‐neutral reactions feature broad substrate scope (>60 examples), good functional‐group tolerance, and facile generation of quaternary centers. Mechanistic studies indicate that the simple palladium complex acts as the visible‐light photocatalyst and radicals are involved in the process.