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Cu/Pd Synergistic Dual Catalysis: Asymmetric α‐Allylation of an α‐CF 3 Amide
Author(s) -
Saito Akira,
Kumagai Naoya,
Shibasaki Masakatsu
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702113
Subject(s) - stereocenter , chemistry , tetrahydropyran , enantioselective synthesis , cyclopropane , tsuji–trost reaction , amide , catalysis , allylic rearrangement , stereochemistry , ligand (biochemistry) , medicinal chemistry , organic chemistry , ring (chemistry) , biochemistry , receptor
Despite the burgeoning demand for fluorine‐containing chemical entities, the construction of CF 3 ‐containing stereogenic centers has remained elusive. Herein, we report the strategic merger of Cu I /base‐catalyzed enolization of an α‐CF 3 amide and Pd 0 ‐catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing a stereogenic carbon center connected to a CF 3 , an amide carbonyl, and a manipulable allylic group. The phosphine complexes of Cu I and Pd 0 engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric α‐allylation of the amide. The stereoselective cyclization of the obtained α‐CF 3 ‐γ,δ‐unsaturated amides to give tetrahydropyran and γ‐lactone‐fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as a new entry to non‐racemic CF 3 ‐containing compounds.