Amine Catalysis with Substrates Bearing N‐Heterocyclic Moieties Enabled by Control over the Enamine Pyramidalization Direction

Abstract

Stereoselective organocatalytic C–C bond formations that tolerate N‐heterocycles are valuable since these moieties are common motifs in numerous chiral bioactive compounds. Such transformations are, however, challenging since N‐heterocyclic moieties can interfere with the catalytic reaction. Here, we present a peptide that catalyzes conjugate addition reactions between aldehydes and nitroolefins bearing a broad range of different N‐heterocyclic moieties with basic and/or H‐bonding sites in excellent yields and stereoselectivities. Tuning of the pyramidalization direction of the enamine intermediate enabled the high stereoselectivity. © WILEY 2020