Enhanced activity of enantioselective (salen)Mn(III) epoxidation catalysts through supramolecular complexation

(Salen)Mn(III) catalysts show increased turnover numbers in the catalytic asymmetric epoxidation of conjugated olefins upon addition of bulky Lewis acids (LA) such as zinc tetraphenylporphyrin (ZnTPP). Up to 3-fold increase in total catalytic activity and at least a 20-fold increase in catalyst stability was observed with a (salen)Mn catalyst bearing pendant 5,5′-bis-pyridyl groups. This latter enhancement is primarily attributed to formation of a coordination triad, which provides steric protection for the catalyst from bimolecular decomposition. Supramolecular complex formation enhanced the catalyst’s stability without compromising its enantioselectivity. © 2001 Elsevier Science B.V. All rights reserved.