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Highly γ‐Selective Arylation and Carbonylative Arylation of 3‐Bromo‐3,3‐difluoropropene via Nickel Catalysis
Author(s) -
Cheng Ran,
Sang Yueqian,
Gao Xing,
Zhang Shu,
Xue XiaoSong,
Zhang Xingang
Publication year - 2021
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.202015921
Subject(s) - carbonylation , regioselectivity , chemistry , catalysis , nickel , bromide , reductive elimination , functional group , combinatorial chemistry , aryl , density functional theory , medicinal chemistry , organic chemistry , computational chemistry , carbon monoxide , alkyl , polymer
A nickel‐catalyzed highly γ‐regioselective arylation and carbonylative arylation of 3‐bromo‐3,3‐difluoropropene has been developed. The reaction proceeds under mild reaction conditions, providing the gem‐difluoroalkenes with high efficiency and good functional group tolerance. The resulting gem‐difluoroalkenes can serve as versatile building blocks for diversified synthesis. Preliminary mechanistic studies and density functional theory calculations reveal that both non‐radical and radical pathways are possible for the reaction, and the radical pathway is more likely. The high γ‐regioselectivity results from the β‐bromide elimination of alkylnickel(II) species or from the reductive elimination of nickel(III) species [(aryl)(CF 2 =CHCH 2 )Ni III (L n )X]. The γ‐selective carbonylation of 3‐bromo‐3,3‐difluoropropene under 1 atm CO gas also provides a new way for nickel‐catalyzed carbonylation.