Cu I -Amidobis(phosphine)-Catalyzed Direct Amidation of Unactivated Alkanes via C(sp 3 )-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 Cu I complex [Cu I { o -Ph 2 PC 6 H 4 CONC 6 H 4 PPh 2 - o } 2 ] (here onward referred to as [PNP-Cu] 2 ). Using this method, C(sp 3 )-N bond formation was achieved through the activation of very challenging C(sp 3 )-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(sp 3 )-N bond formation via direct N-alkylation of phthalimide, sulfonamide, benzamide, and phosphamidate.