CuI-Amidobis(phosphine)-Catalyzed Direct Amidation of Unactivated Alkanes via C(sp3)-H Activation.

Herein, we describe an acid-base-free, sustainable, and efficient method for direct amidation of unactivated alkanes and toluene derivatives, using the dimeric CuI complex [CuI{o-Ph2PC6H4CONC6H4PPh2-o}2] (here onward referred to as [PNP-Cu]2). Using this method, C(sp3)-N bond formation was achieved through the activation of very challenging C(sp3)-H bonds in cycloalkanes, alkenes, allyl groups, and benzyl groups, with tolerance toward ketonic groups, heterocycles, and halide functionalities. One of the precatalysts, (PNHP-Cu-Npht) was isolated and structurally characterized. Isomerization in allyl-functionalized alkanes and selective benzylic alkylation in ketones were observed. This is a novel method for C(sp3)-N bond formation via direct N-alkylation of phthalimide, sulfonamide, benzamide, and phosphamidate.