Evidence of Asymmetric Autocatalysis in Organocatalytic Reactions

Abstract

When product and catalyst are the same: The chiral product 3 of an asymmetric Mannich reaction (see scheme), investigated under various experimental conditions and by calculations, is shown to act as a chiral catalyst for its own formation (autocatalysis). A generally applicable catalytic cycle is proposed to involve equilibria between hydrogen-bonded substrate–product complexes.