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From C 1 to C 3 : Copper‐Catalyzed gem ‐Bis(trifluoromethyl)olefination of α‐Diazo Esters with TMSCF 3
Author(s) -
Wang Qian,
Ni Chuanfa,
Hu Mingyou,
Xie Qiqiang,
Liu Qinghe,
Pan Shitao,
Hu Jinbo
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.202002409
Subject(s) - diazo , trifluoromethyl , carbene , chemistry , catalysis , fluoride , copper , medicinal chemistry , combinatorial chemistry , organic chemistry , inorganic chemistry , alkyl
A Cu‐catalyzed gem ‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF 3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem ‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into “CuCF 3 ” to generate the α‐CF 3 ‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C 1 ‐to‐C 3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐ difluoroalkene intermediates.