Enantioselective Nickel‐Catalyzed Denitrogenative Transannulation En Route to N−N Atropisomers

Nickel‐catalyzed transannulation reactions triggered by the extrusion of small gaseous molecules have emerged as a powerful strategy for the efficient construction of heterocyclic compounds. However, their use in asymmetric synthesis remains challenging because of the difficulty in controlling stereo‐ and regioselectivity. Herein, we report the first nickel‐catalyzed asymmetric synthesis of N−N atropisomers by the denitrogenative transannulation of benzotriazones with alkynes. A broad range of N−N atropisomers was obtained with excellent regio‐ and enantioselectivity under mild conditions. Moreover, density functional theory (DFT) calculations provided insights into the nickel‐catalyzed reaction mechanism and enantioselectivity control.