The first catalytic asymmetric (4+3) cyclization of in situ generated ortho‐quinone methides with 2‐indolylmethanols has been established, which constructed seven‐membered heterocycles in high yields (up to 95 %) and excellent enantioselectivity (up to 98 %). This approach not only represents the first catalytic asymmetric (4+3) cyclization of o‐hydroxybenzyl alcohols, but also enabled an unprecedented catalytic asymmetric (4+3) cyclization of 2‐indolylmethanols. In addition, a scarcely reported catalytic asymmetric (4+3) cyclization of para‐quinone methide derivatives was accomplished.

A facile and efficient protocol for the construction of alkenyl dithiocyanates and alkenyl diselenocyanates has been developed via stereoselective difunctionalization of alkynes with NaSCN or KSeCN at room temperature.

Under cooperative catalysis of iridium and a Brønsted acid, different C4-substituted azlactones react with vinyl benzoxazinones via a formal [4+2] cycloaddition or substitution reaction in a chemo- and stereoselective mode.

An eco-friendly and practical method for the ultrasonic multicomponent synthesis of diverse (Z)-β-iodo vinylthiocyanates from cheap and commercially available alkynes, molecular iodine, and KSCN through an intermolecular H-bonding assistance strategy was developed.

The first metal‐catalyzed C3‐nucleophilic (4+3) cyclization of 2‐indolylmethanols with stable ortho‐quinone methides has been established, which constructed indole‐based seven‐membered heterocycles in high yields (70 %‐98 %) with regiospecificity. This reaction has tackled the challenges in exploring the C3‐nucleophilicity of 2‐indolylmethanols, which will contribute to the chemistry of 2‐indolylmethanols, especially to metal‐catalyzed cyclizations of 2‐indolylmethanols. In addition, this approach will provide a useful method for constructing indole‐based seven‐membered heterocycles with high efficiency and regioselectivity.