DESIGN AND SYNTHESIS OF CHIRAL KETONES FOR CATALYTIC ASYMMETRIC EPOXIDATION OF UNFUNCTIONALIZED OLEFINS

A series of C-2 symmetric chiral ketones were designed and synthesized for catalytic asymmetric epoxidation of unfunctionalized olefins. Amo ng those ketones screened, (R)-7, (R)-9, and (R)-10 were found to be h ighly efficient catalysts for epoxidation of trans-stilbenes with enan tioselectivities in the range of 84-95%. Convincing evidence was provi ded for a spiro transition state of dioxirane epoxidation. Through the O-18-labeling experiment, chiral dioxiranes were found to be the inte rmediates in chiral ketone catalyzed epoxidation reactions.