Asymmetric One‐Pot Mukaiyama Michael/Michael Reaction Catalyzed by Diphenylprolinol Silyl Ether

Abstract

The asymmetric catalytic Mukaiyama Michael reaction between α,β‐unsaturated aldehydes and silyl enol ether derived from a cyclic ketone was catalyzed by diphenylprolinol silyl ether to afford Michael products with excellent diastereo‐ and enantioselectivities. Bicyclo[2.2.2]octanone derivatives can be synthesized as a single isomer in a nearly optically pure form via a two‐step, one‐pot reaction, comprising the sequential Mukaiyama Michael reaction and intramolecular Michael reaction starting from dienol silyl ether and α,β‐unsaturated aldehydes, catalyzed by diphenylprolinol silyl ether. In the second Michael reaction, positive kinetic resolution occurred to increase the enantioselectivity.