Design of new chiral phase-transfer catalysts with dual functions for highly enantioselective epoxidation of alpha,beta-unsaturated ketones.

A new chiral ammonium bromide, 1-Br, possessing diarylmethanol functionality as a substrate recognition site has been designed as a promising, dual-functioning catalyst for the highly enantioselective epoxidation of alpha,beta-unsaturated ketones under mild phase-transfer conditions. For instance, vigorous stirring of a mixture of chalcone, 1-Br (3 mol %), and 13% NaOCl in toluene at 0 degrees C for 24 h gave rise to epoxy chalcone quantitatively with 96% ee. A variety of alpha,beta-unsaturated ketones can also be epoxidized with rigorous stereochemical control, clearly demonstrating the effectiveness and utility of the present system. Further, a successful single-crystal X-ray diffraction analysis of 1-PF6 uncovered its distinctive three-dimensional molecular architecture and provided useful information for postulating the transition state.