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Dual Nickel‐ and Photoredox‐Catalyzed Enantioselective Desymmetrization of Cyclic meso ‐Anhydrides
Author(s) -
Stache Erin E.,
Rovis Tomislav,
Doyle Abigail G.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201700097
Subject(s) - desymmetrization , enantioselective synthesis , homolysis , chemistry , decarbonylation , catalysis , adduct , steric effects , nickel , medicinal chemistry , stereochemistry , organic chemistry , radical
The enantioselective desymmetrization of cyclic meso‐anhydrides with benzyl trifluoroborates under nickel‐photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto‐acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni−C bond homolysis of a Ni II adduct is proposed. This feature allows access to a trans keto‐acid as the major product in high enantioselectivity from a cis meso anhydride.