Construction of remote dual stereocenters by electrochemical cobalt-catalyzed enantioselective desymmetrization

Abstract The enantio- and diastereoselective construction of two stereogenic centers represents a highly attractive objective in synthetic chemistry. Extensive asymmetric catalytic methods have been developed for the formation of vicinal stereocenters. In contrast, the simultaneous construction of two constitutionally distinct stereogenic centers at remote positions in a single asymmetric catalytic step remains very scarce, owing to the lack of reliable models for distant stereochemical induction for both chiral entities. Herein, we report on an electrochemical cobalt-catalyzed asymmetric hydroacylation of enynes by a desymmetrization strategy that enables the enantio- and diastereo-selective construction of remote dual stereocenters. This unified catalytic platform exhibits broad substrate generality and affords four distinct classes of chiral products, each incorporating two chiral elements: 1,6-central/C–C axial chirality, 1,6-central/C–O axial chirality, 1,5-central/[2.2]paracyclophane planar chirality, and 1,5-central/ferrocene planar chirality.