A Comparative Study of Cationic Copper(I) Reagents Supported by Bipodal Tetramethylguanidinyl-Containing Ligands as Nitrene-Transfer Catalysts

Abstract

The bipodal compounds [(TMG 2 biphen N-R )Cu I − NCMe](PF 6 ) (R = Me, Ar (4-CF 3 Ph-)) and [(TMG 2 biphen N-Me )-Cu I −I] have been synthesized with ligands that feature a diarylmethyl-and triaryl-amine framework and superbasic tetramethylguanidinyl residues (TMG). The cationic Cu(I) sites mediate catalytic nitrene-transfer reactions between the imidoiodinane PhI = NTs (Ts = tosyl) and a panel of styrenes in MeCN, to afford aziridines, demonstrating comparable reactivity profiles. The copper reagents have been further explored to execute C−H amination reactions with a variety of aliphatic and aromatic hydrocarbons and two distinct nitrene sources PhI = NTs and PhI = NTces (Tces = 2,2,2-trichloroethylsulfamate) in benzene/HFIP (10:2 v/v). Good yields have been obtained for sec-benzylic and tert-C−H bonds of various substrates, especially with the more electron-deficient catalyst [(TMG 2 biphen N−Ar )Cu I −NCMe](PF 6 ). In conjunction with earlier studies, the order of reactivity of these bipodal cationic reagents as a function of the metal employed is established as Cu > Fe > Co ≥ Mn. However, as opposed to the base-metal analogues, the bipodal Cu reagents are less reactive than a similar tripodal Cu catalyst. The observed fluorophilicity of the bipodal Cu compounds may provide a deactivation pathway.