Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins.

ABSTRACT: We describe the synthetically useful enantioselective addition of Br-CX3 (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)RhII BrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.

SUBMITTER: Chen B 

PROVIDER: S-EPMC5672916 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature