Stereoselective alkoxycarbonylation of unactivated C(sp3)-H bonds with alkyl chloroformates via Pd(II)/Pd(IV) catalysis.
Several examples on Pd-catalysed carbonylation of methyl C(sp3)-H bonds with gaseous CO via Pd(II)/Pd(0) catalysis have been reported. However, methylene C(sp3)-H carbonylation remains a great challenge, largely due to the lack of reactivity of C-H bonds and the difficulty in CO migratory insertion. Herein, we report the stereoselective alkoxycarbonylation of both methyl and methylene C(sp3)-H bonds with alkyl chloroformates through a Pd(II)/Pd(IV) catalytic cycle. A broad range of aliphatic carboxamides and alkyl chloroformates are compatible with this protocol. In addition, this process is scalable and the directing group could be easily removed under mild conditions with complete retention of configuration.
Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Gang
G
Liao
Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Xue-Song
XS
Yin
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Kai
K
Chen
Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Qi
Q
Zhang
Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Shuo-Qing
SQ
Zhang
Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Bing-Feng
BF
Shi
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