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Copper(II) ketimides in sp3 C–H amination
Chemical Science  (IF9.825),  Pub Date : 2021-11-05, DOI: 10.1039/d1sc01990b
Isuri U. Jayasooriya, Abolghasem (Gus) Bakhoda, Rachel Palmer, Kristi Ng, Nour L. Khachemoune, Jeffery A. Bertke, Timothy H. Warren

Commercially available benzophenone imine (HN[double bond, length as m-dash]CPh2) reacts with β-diketiminato copper(II) tert-butoxide complexes [CuII]–OtBu to form isolable copper(II) ketimides [CuII]–N[double bond, length as m-dash]CPh2. Structural characterization of the three coordinate copper(II) ketimide [Me3NN]Cu–N[double bond, length as m-dash]CPh2 reveals a short Cu-Nketimide distance (1.700(2) Å) with a nearly linear Cu–N–C linkage (178.9(2)°). Copper(II) ketimides [CuII]–N[double bond, length as m-dash]CPh2 readily capture alkyl radicals R˙ (PhCH(˙)Me and Cy˙) to form the corresponding R–N[double bond, length as m-dash]CPh2 products in a process that competes with N–N coupling of copper(II) ketimides [CuII]–N[double bond, length as m-dash]CPh2 to form the azine Ph2C[double bond, length as m-dash]N–N[double bond, length as m-dash]CPh2. Copper(II) ketimides [CuII]–N[double bond, length as m-dash]CAr2 serve as intermediates in catalytic sp3 C–H amination of substrates R–H with ketimines HN[double bond, length as m-dash]CAr2 and tBuOOtBu as oxidant to form N-alkyl ketimines R–N[double bond, length as m-dash]CAr2. This protocol enables the use of unactivated sp3 C–H bonds to give R–N[double bond, length as m-dash]CAr2 products easily converted to primary amines R–NH2 via simple acidic deprotection.