Recent Advances in the Pd‐Catalyzed Coupling of Arylhydrazines and Ammonium Salts via C−N Bond Cleavage

Abstract

Both arylhydrazines and quaternary ammonium salts are readily accessible or commercially available chemicals that show versatile reactivity in Pd-catalyzed coupling reactions via CÀ N bond cleavage. A tremendous array of coupling reactions involving reaction partners such as organoborons, aryl silanes, alkenes, alkynes, arylation or alkylation reagents in CÀ H functionalization and carbonylation reactions are summarized, in which arylhydrazines or quaternary ammonium salts function as aryl or alkyl donors. This account mainly focuses on recent advances in Pd-catalyzed coupling reactions with arylhydrazines or quaternary ammonium salts via CÀ N bond cleavage, including mechanistic elucidations.

Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes

“…C(sp 2 )−C(sp 2 ) Cross-Coupling. Arylhydrazines are commonly known to engage as either the electrophilic 53 or the nucleophilic components (through the transient diimide species; vide supra) 5 in C(sp 2 )−C(sp 2 ) cross-couplings with concomitant release of dinitrogen. Considering that we showed in our previous study that the ligand in the palladium(II) precatalyst significantly influences the chemoselectivity of the reaction, 50 we therefore foresaw a different catalytic system that would selectively furnish the denitrogenated biaryl compounds with the N-aryl-N′-silyldiazenes serving as aryl pronucleophiles.…”

Radical coupling reactions of hydrazinesviaphotochemical and electrochemical strategies

“…2 In the past decades, they have been widely used in transition metal-catalysed coupling reactions via the C–N bond cleavage process for the formation of carbon–carbon and carbon–heteroatom bonds. 3…”

Palladium-catalysed deaminative/decarboxylative cross-coupling of organoammonium salts with carboxylic acids

“…The catalytic conversion of organoammonium salts is important for the utilization of amines. 10,11 Very recently, the deaminative and decarboxylative cross-coupling reaction of reactive 2-oxocarboxylic acids with aromatic ammonium salts was achieved using Ni and electrocatalysis. The reaction can be used to produce various aromatic acyl derivatives.…”