Enantioselective Organocatalytic Allylic Amination

Abstract

A new strategy for catalytic enantioselective allylic amination based on organocatalysis has been developed. Using a commercially available organocatalyst we demonstrate a direct highly enantioselective allylic electrophilic functionalization of alkylidene cyanoacetates and malononitriles with azodicarboxylates. The reaction is broad in scope and proceeds in high yields and with enantioselectivities up to 99%. Furthermore, we demonstrate the synthetic utility of the optically active products formed: highly diastereoselective Diels-Alder reaction, reduction, and formation of optically active building blocks, which are found in various important bioactive compounds such as quinacrine, chloroquine, and analogues thereof.