Photochemical Deracemization of Chiral Alkenes via Triplet Energy Transfer

A visible-light-mediated, enantioselective approach to axially chiral alkenes is described. Starting from a racemic mixture, a major alkene enantiomer is formed due to selective triplet energy transfer from a catalytically active chiral sensitizer. A catalyst loading of 2 mol % was sufficient to guarantee consistently high enantioselectivities and yields (16 examples, 51%-quant., 81-96% ee). NMR studies and DFT computations revealed that triplet energy transfer is more rapid within the substrate-catalyst complex of the minor alkene enantiomer. Since this enantiomer is continuously racemized, the major enantiomer is enriched in the photostationary state.

Automated summary

This study describes a visible-light-mediated, enantioselective approach for the synthesis of axially chiral alkenes. By selectively transferring triplet energy from a racemic mixture, a major alkene enantiomer is formed. A small catalyst loading ensures consistently high selectivities and yields.