A palladium-catalyzed dearomative syn-1,4-aminofunctionalization protocol using readily available arenes has been developed. This one-pot procedure utilizes arene–arenophile para-cycloadducts, formed via visible-light-mediated [4+2]-photocycloaddition, which undergoes formal allylic substitution with carbon-, nitrogen-, and oxygen-based nucleophiles. The reaction conditions permit a wide range of arenes, including naphthalene derivatives, benzene, and hereoarenes. This process can also be used for asymmetric desymmetrization, delivering products with high enantioselectivity. Moreover, the resulting syn-1,4-aminofunctionalized products are amenable to further derivatizations, which effectively installed other functionalities onto the unsaturated carbocycles. Overall, these novel dearomative syn-1,4-aminofunctionalizations offer straightforward access to complex structures from simple arenes, thus enabling the rapid formation of highly functionalized building blocks that are otherwise difficult to prepare through existing dearomative strategies.

Palladium-catalyzed dearomative syn-1,4-aminofunctionalizations

256th National Meeting (2018)

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