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Palladium‐Catalyzed Negishi Cross‐Coupling Reaction of Difluoroiodomethane with Arylzinc Reagents
Author(s) -
Nitta Junki,
Motohashi Hirotaka,
Aikawa Kohsuke,
Mikami Koichi
Publication year - 2019
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201900106
Subject(s) - xantphos , chemistry , transmetalation , negishi coupling , palladium , reagent , catalysis , reductive elimination , oxidative addition , combinatorial chemistry , organic chemistry
The catalytic difluoromethylation of arylzinc reagents with difluoroiodomethane in the presence of Pd 2 (dba) 3 /Xantphos is described to produce difluoromethyl products. Mechanistic investigations reveal that the oxidative addition of difluoroiodomethane to [(Xantphos)Pd 0 ] provides trans ‐[(Xantphos)Pd II (I)CF 2 H], which is subsequently transformed to cis ‐[(Xantphos)Pd II (Ph)CF 2 H] through transmetalation of phenylzinc. Next, reductive elimination occurs ( t 1/2 =44.7 min at −10 °C) to give PhCF 2 H. The structural changes in [(Xantphos)Pd II (Ph)CF 2 H] from trans to cis facilitates reductive elimination of PhCF 2 H.