Details

Autor(en) / Beteiligte

• Jayasooriya, Isuri U
• Bakhoda, Abolghasem (Gus)
• Palmer, Rachel
• Ng, Kristi
• Khachemoune, Nour L
• Bertke, Jeffery A
• Warren, Timothy H

Titel

Copper() ketimides in sp C-H amination

Ist Teil von

• Chemical science (Cambridge), 2021-12, Vol.12 (47), p.15733-15738

Erscheinungsjahr

2021

Quelle

EZB-FREE-00999 freely available EZB journals

Beschreibungen/Notizen

• Commercially available benzophenone imine (HN&z.dbd;CPh 2 ) reacts with β-diketiminato copper( ii ) tert -butoxide complexes [Cu II ]-O t Bu to form isolable copper( ii ) ketimides [Cu II ]-N&z.dbd;CPh 2 . Structural characterization of the three coordinate copper( ii ) ketimide [Me 3 NN]Cu-N&z.dbd;CPh 2 reveals a short Cu-N ketimide distance (1.700(2) Å) with a nearly linear Cu-N-C linkage (178.9(2)°). Copper( ii ) ketimides [Cu II ]-N&z.dbd;CPh 2 readily capture alkyl radicals R&z.rad; (PhCH(&z.rad;)Me and Cy&z.rad;) to form the corresponding R-N&z.dbd;CPh 2 products in a process that competes with N-N coupling of copper( ii ) ketimides [Cu II ]-N&z.dbd;CPh 2 to form the azine Ph 2 C&z.dbd;N-N&z.dbd;CPh 2 . Copper( ii ) ketimides [Cu II ]-N&z.dbd;CAr 2 serve as intermediates in catalytic sp 3 C-H amination of substrates R-H with ketimines HN&z.dbd;CAr 2 and t BuOO t Bu as oxidant to form N -alkyl ketimines R-N&z.dbd;CAr 2 . This protocol enables the use of unactivated sp 3 C-H bonds to give R-N&z.dbd;CAr 2 products easily converted to primary amines R-NH 2 via simple acidic deprotection. Commercially available benzophenone imine (HN&z.dbd;CPh 2 ) reacts with β-diketiminato copper( ii ) tert -butoxide complexes [Cu II ]-O t Bu to form isolable copper( ii ) ketimides [Cu II ]-N&z.dbd;CPh 2 that serve as intermediates in catalytic sp 3 C−H amination via radical relay.