Palladium-Catalyzed Oxidative Amination of Unactivated Olefins with Primary Aliphatic Amines

Abstract

Direct coupling of unactivated olefins with primary alkylamines is considered to be an efficient but unknown method for the construction of complex amines. Herein we report a catalytic intermolecular oxidative amination of unactivated olefins with primary aliphatic amines based on the combination of a palladium catalyst, a bidentate phosphine ligand, and duroquinone. A range of secondary allylic amines were obtained in good yields with excellent regio- and stereoselectivity. Mechanistic control experiments revealed that the reaction proceeds by allylic C(sp3)–H activation and nucleophilic amination. The utility of the protocol is further demonstrated with the late-stage modification and streamlined synthesis of drug molecules.

Cooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline

“…In particular, palladium-catalyzed allylic C–H bond oxidation reactions have been extensively investigated (Fig. 2a ) 14 – 21 . In a seminal report, White and colleagues reported the catalytic allylic C–H cleavage of terminal olefins catalyzed by Pd(II)/bis-sulfoxide 22 .…”

Thermal/photochemical micro-flow probe system for direct C–H bond functionalization of biologically active molecules

“…Amines are key fragments in many natural products, 1,2 pharmaceuticals, 3,4 and agrochemicals. 5,6 Nearly 47% of the top 200 prescription medicines in 2022 contained an amine moiety (Scheme 1a).…”

Heterogenized molecular Pd(ii) catalyst on ultrathin 2D metal–organic frameworks with nanoflower-like morphology for isonitrile-involved cyclization reaction

“…With high reactivity and selectivity, palladium (Pd) based catalysts dominate in the field of organic synthesis chemistry, including oxidation reactions, [1][2][3][4][5] C-C/C-X cross-coupling reactions, [6][7][8][9] hydrogenation reaction, 10,11 and so on. Generally, a homogeneous Pd-mediated catalytic process is conducive to the sufficient contact between catalytic sites and reactants, which can not only maximize the use of Pd active sites, but also provide a flexible reaction space, so as to achieve high catalytic efficiency and high selectivity.…”