10.1002/anie.201807873
Angewandte Chemie International Edition
COMMUNICATION
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methyl complexes (CF3-M) can serve as precursors for metal
difluorocarbenes (M=CF2)[8e,22]
,
we propose that copper
difluorocarbene (Cu=CF2) can be the possible intermediate in the
transformation from CuCF3 to CuC2F5 (Scheme 4, path a).[23]
In conclusion, a C1 to C2 process was achieved, using
TMSCF3 as a convenient pentafluoroethyl source. This reaction
proceeds via in situ generation of CuCF3, followed by sponta-
neous transformation to CuC2F5 in high yield and selectivity. This
CuC2F5 species could undergo coupling reaction with aryl iodides
to provide aromatic pentafluoroethyl products in moderate to
excellent yields. This protocol not only represents the first prac-
tical and efficient pentafluoroethylation reaction of aryl iodides
using TMSCF3 reagent, it also opens a new door to the efficient
homologation of fluorocarbon chains that has been previously
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Acknowledgements
Financial support of this work by the National Basic Research
Program of China (2015CB931900, 2016YFB0101200), the
National Natural Science Foundation of China (21632009,
21421002, 21472221), the Key Program of the Chinese Acade-
my of Sciences (KGZD-EW-T08), the Key Research Program of
Frontier Sciences of CAS (QYZDJ-SSW-SLH049), the Shanghai
Rising-Star Program (16QA1404600), and the Youth Innovation
Promotion Association CAS (2014231) is gratefully acknowl-
edged.
Keywords: pentafluoroethylation • trifluoromethyltrimethyl silane
• copper • difluorocarbene • homologation
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