Copper‐Catalyzed Oxidative C(sp³)−H/N−H Cross‐Coupling of Hydrocarbons with P(O)−NH Compounds: the Accelerating Effect Induced by Carboxylic Acid Coproduct

Abstract

An chelation-assisted oxidative C (sp 3 )À H/NÀ H cross coupling of hydrocarbons with P(O)À NH compounds using copper acetate as catalyst is described. The results of kinetic experiments, mechanistic studies and DFT calculations demonstrate the importance of acetic acid coproduct as an additive for promoting the formation of intermediate bis((diphenylphosphoryl)(quinolin-8yl)amino)copper (6), and consequently accelerating the construction of C(sp 3 )À N bond. The reaction proceeded efficiently with a wide array of hydrocarbons and P(O)À NH compounds, and the rate acceleration induced by the acetic acid coproduct have been repeatedly proven. Furthermore, the efficiency of small-scale reaction could be retained upon gram-scale synthesis in a continuous manner.

Selenium-catalyzed allylic C–H phosphoramidation of alkenes

“…Therefore, recent progress in this field has been demonstrated by new synthetic strategies, such as Staudinger-type reactions of organic azides with phosphite esters 7 and transition metal-catalyzed aromatic and benzylic C–H phosphoramidations. 8 Despite the significant advances made in this field, current C–H phosphoramidation protocols remain limited to aryl and benzyl substrates. Meanwhile, direct modification of complex natural products and pharmaceuticals to incorporate phosphoramidates remains challenging.…”