Dysprosium(III)-Catalyzed Ring-Opening of meso-Epoxides: Desymmetrization by Remote Stereocontrol in a Thiolysis/Elimination Sequence

Abstract

An unprecedented asymmetric desymmetrization of meso-epoxides, derived from cyclopentene-1,3-diones, with 2-mercaptobenzothiazoles has been realized. It was efficiently catalyzed by a chiral Dy(III) /N,N'-dioxide complex through a thiolysis/elimination sequence. This remote stereocontrol strategy provides facile access to synthetically versatile cyclopentene derivatives bearing an all-carbon quaternary stereogenic center in high yield and excellent enantioselectivity. Intriguingly, optically active thiophene could be readily generated from the obtained product through an efficient one-pot protocol.

Keywords: N ligands; asymmetric catalysis; dysprosium; enantioselectivity; heterocycles.