Breaking The Monotony: Cobalt and Maleimide as a New Entrant to the Catellani Reaction

Abstract

A catalytic system was discovered for the intramolecular C-H amidation of N-phenoxy acetamide derivatives. For the first time, a cobalt catalyst was employed for the Catellani reaction. Additionally, a monocyclic olefin, maleimide, was used as a transient mediator in place of bicyclic norbornenes. Maleimide promotes a Co(III) intermediate to undergo oxidative addition into the O–N bond to form a Co(V) nitrene species and subsequently directs nitrene addition to the ortho position. A plausible mechanism for the transformation is proposed, supported by experimental and density functional theory (DFT) computational studies. Further, the synthetic utility of this methodology was demonstrated via the ortho-amidation of estrone.