Intermediate Control: Unlocking Hitherto Unknown Reactivity and Selectivity in N-Conjugated Allenes and Alkynes

Abstract

Controlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C–C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies. In this regard, our group, alongside others, has established some new approaches that have emerged as a suitable platform for the synthesis of functionalized enamides. This Account reviews recent developments in the field, highlighting new modes of reactivity and selectivity, atom-economical functionalizations, and strategies for regio- and stereocontrol, while providing mechanistic insights into related transformations.