Efficient Heterogeneous Asymmetric Catalysis of the Mukaiyama Aldol Reaction by Silica‐ and Ionic Liquid‐Supported Lewis Acid Copper(II) Complexes of Bis(oxazolines)

Abstract

AbstractLewis acid complexes based on copper(II) and an imidazolium‐tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1‐methoxy‐1‐trimethylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2 min compared with only 55 % conversion after 60 min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3‐hydroxy‐1,3‐diphenylbutan‐1‐one as a by‐product. Supporting the catalyst on silica or an imidazolium‐modified silica using the ionic liquid or in an ionic liquid‐diethyl ether system completely suppressed the formation of this by‐product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee.