Copper Catalyzed C–N Cross-Coupling Reaction of Aryl Boronic Acids at Room Temperature through Chelation Assistance

Abstract

A copper-catalyzed selective C-N cross-coupling has been developed based on chelation-assisted amidation of readily available aryl boronic acids at room-temperature under open-flask conditions. The reaction is scalable and tolerates a wide spectrum of functional groups delivering fully substituted unsymmetrical amides in high yields (up to 96%). The C-N cross coupling also established with aryl silanes, extending the palette of coupling partners of this strategy.

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

“…Note that the arylation of the NH of the picolinamide part was also reported with boronic acids (not shown). 575 …”

Direct Introduction of Sulfonamide Groups into Quinoxalin‐2(1H)‐ones by Cu‐Catalyzed C3‐H Functionalization

“…Initially, the Cu(I) catalyst A reacts with peroxydisulfate B to produce active Cu(II) species C , SO 4 2− and SO 4 .− radical anion ( D ), and D abstracts a hydrogen atom from sulfonamide 2 a to generate HSO 4 − and the corresponding sulfonamide radical F . Subsequently, the coordination of C with the nitrogen atom of the C=N bond in the quinoxalin‐2(1 H )‐one substrate leads to the polarization of the C=N double bond and gives the active species E , which undergoes an addition with the sulfonamide radical F to provide the key intermediate G . Finally, the intermediate G goes through a single‐electron transfer and deprotonation in succession to afford the target product 3 a , with regenerating the copper(I) catalyst A to complete the catalytic cycle.…”

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

“…Recently, the development of chelation‐assisted transition‐metal catalysis has provided a new complementary route for facile construction of various C−N bonds . Reactions of copper‐chelation system can be performed even at room temperature ,,. The intramolecular dehydrogenative amidation protocol have been well established by researchers such as Shi, Kanai, Ge,, Shi, and Bedford (Scheme c).…”