Dearomative syn-1,2-Diamination of Benzene and Naphthalene

Dedicated to Prof. Sarah Reisman on occasion of winning the 2019 Dr. Margaret Faul Women in Chemistry Award

Abstract

We report the palladium-catalyzed, dearomative syn-1,2-diamination of the non-activated arenes benzene and naphthalene using aryl isocyanates. This reaction proceeds with exclusive syn-1,2-selectivity and provides a complementary regio- and stereoselectivity to previously described arenophile-based transformations. The products are amenable to further synthetic elaboration, including selective diene functionalization and heterocycle cleavage. Overall, this dearomatization provides synthetic access to unprecedented saturated nitrogen-containing heterocyclic motifs and syn-1,2-diaminated cyclohexane products.

Key words

dearomatization - amine - heterocycle - palladium - catalysis - isocyanate

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