Skeletal Editing of (Hetero)Arenes Using Carbenes.

Abstract

(Hetero)arenes continue to prove their indispensability in pharmaceutical engineering, materials science, and synthetic chemistry. As such, the controllable modification of biologically significant (hetero)arenes towards diverse more-potent complex molecular scaffolds through peripheral and skeletal editing has been considered a challenging goal in synthetic organic chemistry. Despite many excellent reviews that have discussed peripheral editing (i.e., C-H functionalization) of (hetero)arenes, their skeletal editing via single atom insertion, deletion, or transmutations has so far been less discussed. In this review, we tried to summarize and depict the state-of-the-art skeletal editing reactions on heteroarenes using carbenes, with a focus on general mechanistic considerations and the potential application of this transformation for the synthesis of natural products. The potential opportunities and inherent challenges encountered while developing these strategies have also been highlighted.