N-Heterocyclic carbene (NHC) organocatalysis: from fundamentals to frontiers

Abstract

N-Heterocyclic carbenes (NHCs) have been used as organocatalysts for a multitude of C–C and C–heteroatom bond-forming reactions. They enable diverse modalities of activating a wide range of structurally distinct substrate classes and allow access to electronically distinct intermediates. The easy tunability of the NHC scaffold contributes to its versatility. Recent years have witnessed a surge of interest in various organocatalytic reactions of NHCs, leading to the forays of NHC catalysis into the relatively newer domains such as reactions involving radical intermediates, atroposelective synthesis, umpolung of electrophiles other than aldehydes, and the use of NHCs as non-covalent templates for enantioinduction. This tutorial review provides an overview of various important structural features and reactivity modes of NHCs and delves deep into some frontiers of NHC-organocatalysis.