Manganese-Catalyzed [3 + 2] Cyclization of Ketones and Isocyanates via Inert C–H Activation

Abstract

Stoichiometric cyclomanganation of aromatic ketones and further reactions of the thus-formed manganacycles with isocyanates were first reported by Kaesz and Liebeskind in 1975 and 1990, respectively. The buildup of a closed manganese catalytic cycle for the reaction of ketones and isocyanates remains an unsolved problem. Herein, an unprecedented trio of Me2Zn/AlCl3/AgOTf is developed to build up manganese catalysis, which enables the [3 + 2] cyclization of ketones with isocyanates via inert C–H activation to access 3-alkylidene phthalimidines in a straightforward manner unachieved by other transition metal catalyses.

Topics & Concepts