Catalytic vs. uncatalyzed [2 + 2] photocycloadditions of quinones with alkynes

Abstract

Photoreactions of quinones with alkynes under catalytic and non-catalytic conditions were studied. In contrast to recent reports, simple irradiation with blue light is sufficient to trigger [2 + 2] photocycloadditions, which afford either fused cyclobutenes or reactive para-quinone methides (p-QMs) depending on the quinone structure. Revision of the chemo- and regioselectivity of the uncatalyzed photoreactions provided useful insight into their overlooked relatedness to the recently developed catalytic protocols. Experimental evidence indicates that the reactivity of the photochemically generated p-QMs is sufficient to perform uncatalyzed reactions with nucleophiles, which can help to explain the existing transformations and develop new cascade transformations involving quinones and alkynes.