Enantioselective epoxidation of olefins with molecular oxygen catalyzed by gold(III): A dual pathway for oxygen transfer

Abstract A chiral gold(III) complex has been prepared that performs the epoxidation of olefins in the presence of O 2 , PhIO, or bleach. Catalytic experiments with 18 O show that O 2 is activated on the catalyst and can be directly incorporated into the epoxide through a non-radical mechanism that probably involves formation of gold, oxo, or peroxo species. In addition to this, there is a parallel radical mechanism operating that yields α , β -unsaturated ketones and alcohols as subproducts. Electrochemical and UV–Vis experiments confirmed the occurrence of a Au(III)/Au(I) redox cycle during the catalytic epoxidation in a mechanism sustained by molecular oxygen.