Rh‐Catalyzed Direct Amination of Unactivated C(sp³)−H bond with Anthranils Under Mild Conditions

Abstract

C-N Bond formation is of great significance due to the ubiquity of nitrogen-containing compounds. Here, a mild and efficient Rh(III) -catalyzed C(sp(3) )-H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C-H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H-D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented.

A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

“…Jiao and Li/Lan reported the amination of 8-methylquinolines and 2-ethylpyridines using anthranils under very similar conditions ( Scheme 134A ). 802 , 803 A notable point, apart from various functionalities tolerated on both coupling partners, is the possibility to employ 8-ethylquinolines as substrates, which are generally not reactive.…”

Palladium-Catalyzed Direct Intermolecular Amination of Unactivated Methylene C(sp3)–H Bonds with Azodiformates via Bidentate-Chelation Assistance

“…In the past decades, significant advances have been made in the direct conversion of C­(sp 2 )–H or C­(sp 3 )–H bonds to C–N bonds. − However, direct catalytic functionalization of intermolecular unactivated sp 3 hybridized C–H amination reaction still remains a great challenge in synthetic chemistry. Since the seminal work of Che and Yu on palladium-catalyzed C­(sp 3 )–H amination of O-methyl oximes has received special attention, because of its high regioselectivity and atom efficiency, only few examples of this palladium-catalyzed intermolecular unactivated C­(sp 3 )–H amination process were individually reported (see Scheme A).…”

Intermolecular C(sp3)−H Amination Promoted by Internal Oxidants: Synthesis of Trifluoroacetylated Hydrazones

“…Recently, internal oxidants such as N ‐fluorobenzenesulfonimide (NFSI), iminoiodinane, hydroxylamine derivatives, and anthranil‐promoted intermolecular C(sp 3 )−H bond amination were investigated by different groups; especially for the attractive intermolecular benzylic C(sp 3 )−H bond amination –. However, owing to the insufficiently activated nature of the benzylic C(sp 3 )−H bond, these amination reactions usually need transition‐metal catalysts, directing groups, high temperature, and/or long reaction times to ensure reactivity and selectivity, and such reactions often lead to the formation of a C−N single bond (Scheme a).…”