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Rhodium‐Catalyzed Enantioselective Radical Addition of CX 4 Reagents to Olefins
Author(s) -
Chen Bo,
Fang Cheng,
Liu Peng,
Ready Joseph M.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201704074
Subject(s) - enantioselective synthesis , rhodium , chemistry , catalysis , bromine , reagent , olefin fiber , combinatorial chemistry , stereochemistry , organic chemistry
We describe the synthetically useful enantioselective addition of Br−CX 3 (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom‐transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer‐sphere bromine abstraction from a [(bisphosphine)Rh II BrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.