Palladium-Catalyzed Ortho-Selective C–H Oxidative Carbonylation of N-Substituted Anilines with CO and Primary Amines for the Synthesis of o-Aminobenzamides

Abstract

An efficient, one-pot strategy with high selectivity and high atom economy for the synthesis of o-aminobenzamides has been developed via palladium-catalyzed ortho-selective C-H oxidative carbonylation of N-substituted anilines with CO and primary amines. A wide range of N-substituted anilines and primary amines can be tolerated in this transformation to afford the corresponding o-aminobenzamides in moderate to excellent yields under mild conditions.

Palladium-catalyzed oxidative dehydrogenative carbonylation reactions using carbon monoxide and mechanistic overviews

“…In 2016, the group of Zhang reported a practical intermolecular aminocarbonylation of anilines for the construction of o-aminobenzamides (Scheme 21). 29 The employment of C-H activation for aminocarbonylation with CO as C1 source is an elegant solution for the synthesis of amides. In this work, both aromatic and aliphatic primary amines were utilized as the coupling partners.…”

Transition-Metal-Catalyzed Intermolecular C–H Carbonylation toward Amides

“…In 2016, Zhang and co-workers developed an efficient palladium-catalyzed directed oxidative intermolecular C-H aminocarbonylation of N-alkylanilines with Cu(OAc) 2 and O 2 as the oxidants (Scheme 2a). 21 The reaction exhibits excellent ortho-selectivity and monocarbonylation, affording various ortho-aminobenzamides in good yields from primary amines. The ortho-selectivity might result from the formation of an ortho-aminoaryl-palladium dimer intermediate.…”

Palladium‐Catalyzed Aerobic Oxidative Carbonylation of C–H Bonds in Phenols for the Synthesis of p‐Hydroxybenzoates

“…Nowadays, directing‐group‐assisted carbonylation of simple C–H bonds has emerged as an ideal strategy, through the introduction of carbon monoxide, to construct a variety of carbonyl compounds. Numerous directing groups such as amides, amines, heteroatoms and hydroxy groups have been used for C–H bond carbonylation . However, most progress has been achieved with compounds containing directing groups and with the use of hazardous metals and oxidants such as copper, silver salts or peroxides, which are undesirable from a green chemistry point of view.…”