Comprehensive Summary Polysubstituted indoles, integral to pharmaceuticals and bioactive natural products, highlight the strategic importance of indole multifunctionalization in drug discovery. This review comprehensively summarizes the recent advances in multifunctionalization reactions of indoles, focusing on the development of three key methodologies: cyclization, di‐, and trifunctionalization, while simultaneously providing an organized framework for understanding catalytic system development, regioselectivity control mechanisms, and cascade reaction design paradigms in this field. Specifically, the content delves into various catalytic systems, encompassing transition metal, metal‐free, organic, and photo/electrochemical approaches for indole multifunctionalization. Particular emphasis is placed on elucidating regio‐ and chemo‐selectivity patterns across various indole sites, along with considerations of orthogonal functional group compatibility. By addressing the absence of comprehensive reviews in this field, this review aims to serve as a valuable reference for advancing indole chemistry, while inspiring new breakthroughs and innovations that will drive the field to new heights.
Zhang et al. (Thu,) studied this question.