Iridium‐Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Benzene Derivatives

Guided by the mechanistic insights from computational studies, we have developed an Ir‐catalyzed asymmetric intramolecular allylic dearomatization reaction of benzene derivatives. Under the optimized conditions consisting of a readily available Ir catalyst, a series of spiro[4.5]cyclohexadiene compounds were delivered in reasonable yields (up to 79 %) with good enantioselectivity (up to 99 % ee ). The introduction of a malonate diester‐type substituent serves as a key strategy to guide the nucleophilic reactivity of the benzene ring.