Copper-Catalyzed Intermolecular C(sp²)–H Amination with Electrophilic O-Benzoyl Hydroxylamines

Abstract

A copper-catalyzed intermolecular electrophilic amination of benzamides with O-benzoyl hydroxylamines was achieved with the assistance of an 8-aminoquinolyl group. With this protocol, good compatibility was observed for a variety of aryl amides and heteroaryl amides, and excellent tolerance with various functional groups was achieved. Significantly, the monoaminated product was overwhelmingly delivered under the simple reaction conditions. Preliminary mechanistic investigations suggested that a radical pathway should be excluded and C–H activation be potentially the rate-determining step.

Palladium-Catalyzed Chelation-Assisted Aldehyde C–H Bond Activation of Quinoline-8-carbaldehydes: Synthesis of Amides from Aldehydes with Anilines and Other Amines

“…During the past decades, transition metal-catalyzed unactivated C–H bond functionalization has been the key tool for synthetic organic chemists for the site-selective construction of C–C and C-heteroatom bonds . Enormous progress has been made in chelation-assisted arene C–H activation, as compared to aldehyde C–H bond activation, which later mostly works using expensive Rh catalysts.…”

Pd-Catalyzed Aryl C–H Amination with Diaziridinone

“…In such studies, we have found that N -(quinolin-8-yl)­benzamides 10 can be efficiently aminated with di- t -butyldiaziridinone ( 1 ) to provide a variety of anthranilic amides 11 (Scheme ). C–H Amination of 10 has been extensively demonstrated with Cu, Fe, Ni, Co, etc., but not with Pd. Anthranilic acid moieties are also present in various biologically and chemically significant compounds (Figure ).…”