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Defluoroalkylation of sp 3 C−F Bonds of Industrially Relevant Hydrofluoroolefins
Author(s) -
Phillips Nicholas A.,
Coates Gregory J.,
White Andrew J. P.,
Crimmin Mark R.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000636
Subject(s) - boron , alkene , chemistry , reagent , nucleophile , carbene , electrophile , bond cleavage , catalysis , medicinal chemistry , trifluoromethyl , organic chemistry , alkyl
A simple, one‐pot procedure is reported for the selective defluoroalkylation of trifluoromethyl alkene derivatives with aldehydes and ketones. The reaction sequence allows construction of a new C−C bond in a highly selective manner from a single sp 3 C−F bond of a CF 3 group in the presence of sp 2 C−F bonds. The scope incorporates industrially relevant fluorocarbons including HFO‐1234yf and HFO‐1234ze. No catalyst, additives or transition metals are required, rather the methodology relies on a recently developed boron reagent. Remarkably, the boron site of this reagent plays a dual role in the reaction sequence, being nucleophilic at boron in the C−F cleavage step (S N 2’) but electrophilic at boron en route to the carbon–carbon bond‐forming step (S E 2’). The duplicitous behaviour is underpinned by a hydrogen atom migration from boron to the carbon atom of a carbene ligand.