Sulfonyl Azoles in the Synthesis of 3‐Functionalized Azole Derivatives

Sulfonyl indoles, as well as related azolyl derivatives, have been recently introduced in synthesis as stable precursors of reactive indolenine intermediates. This personal account reports on the discovery of sulfonyl azoles and their practical utilization in many synthetic processes for the preparation of functionalized 3‐substituted indoles, indazoles, and pyrroles. The indolenine intermediates obtained by treatment of sulfonyl azoles with Brønsted bases or Lewis acids can be considered as vinylogous imino derivatives that can be made to react with different nucleophilic reagents. These include organometallic reagents, reducing agents, stabilized carbanions, and heteronucleophiles. The controlled and mild conditions for the generation of indolenines from sulfonyl azoles make these substrates particularly useful in asymmetric synthesis, exploiting organo‐ or metal‐catalyzed processes. Although less exploited, sulfonyl indoles can also be involved in photochemical processes for the preparation of polycyclic derivatives.