Abstract

AbstractGuided 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.

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