Copper‐Catalyzed Cascade N‐Dealkylation/N‐Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants

Abstract

A novel tandem N‐dealkylation and N‐methyl aerobic oxidation of tertiary aromatic amines to N‐arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N‐methylarylamines to N‐arylformamides.

Hexamethyldisilazane‐Mediated Synthesis of N‐Formamides, Benzimidazoles and Quinazolinones Using N,N‐Dimethylformamide as a C1 Source

“…The authors have cited additional references within the Supporting Information. [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]…”

Alkali-Driven Photoinduced N-Dealkylation of Aryl Tertiary Amines and Amides

“…N-dealkylation is an important transformation in medicinal, agrochemical, biological, and synthetic chemistry because of its wide applications in identification and synthesis of drug metabolites and complex natural product constructions. − The general chemical methods are commonly used for the N-dealkylation of tertiary amines, including transition-metal-catalyzed N-dealkylation, − electrochemical N-dealkylation, − and photochemical N-dealkylation. − Transition-metal-catalyzed N-dealkylation gives the general reaction mechanism that the α position of N , N -dimethyl aryl amines first loses a hydride ion and then the formed iminium ion is hydrolyzed to the ammonium ion, which subsequently loses a proton to form the final N-dealkylation product (Scheme a). , Visible light photoredox catalysis has been established as an elegant method because it allows for the construction of new chemical bonds under mild reaction conditions that typically feature low catalyst loadings, ambient reaction temperatures, and irradiation with either sunlight or standard household light. Different photochemical N-dealkylation methods using various photocatalysts have been developed for the synthesis of various N-dealkylated chemicals.…”