The highly efficient construction of complicated heterocyclic frameworks in an atom‐ and step‐economic manner is still one of the cores of synthetic chemistry. Dearomatization reactions show the unique advantage for the construction of functionalized heterocycles and have attracted widespread attention over the past two decades. The metal‐free approach has proved to be a green and sustainable paradigm for the synthesis of spirocyclic, polycyclic and heterocyclic scaffolds, which are widely present in natural products and bioactive molecules. In this review, the advances in the recent six years (2017–2023) in metal‐free dearomatization reactions are highlighted. Emphasis is placed on developments in the field of organo‐catalyzed dearomatization reactions, oxidative dearomatization reactions, Brønsted acid‐ or base‐promoted dearomatization reactions, photoredox‐catalyzed dearomatization reactions, and electrochemical oxidation dearomatization reactions.

Propargylamines are valuable molecules in medicinal chemistry and organic synthesis. A 3 reaction is straightforward access to construct propargylamine and its derivatives. Here we report operationally simple catalytic domino A 3 -coupling/aza-Michael addition of a primary amine, formaldehyde solution, an alkyne, and an olefin using copper as a catalyst to produce a series of functionalized propargylamines in moderate to excellent yields. This protocol involves a competition between aza-Michael addition and Mannich reaction. By changing the amount loading of amines to control the process of Mannich reaction is the key procedure of increasing the selectivity.

A novel strategy for the synthesis of various N-alkenylisoquinolinones is reported, which features broad functional group tolerance, and good chemoselectivity. This reaction proceeds through a sequential palladium-catalyzed cyclization and C4−O...