NaOTs-promoted transition metal-free C–N bond cleavage to form C–X (X = N, O, S) bonds

Abstract

The direct transformation of the C–N bond of amides to yield secondary amides, esters, and thioesters remains a challenge in organic synthesis. Here, we present a simple and efficient approach...

Transition-metal-catalyst-free reaction of amides and acetonitriles: synthesis of β-ketonitriles

“…24 The use of alcohols or thiols in the reaction with amides has also been developed to yield the corresponding esters and thioesters. 25 The Szostak group reported the transition-metal-free transamidation of unactivated amides; 26 however, examples involving carbon nucleophiles under metal-free conditions were not listed (Scheme 1B-a). Reportedly, protocols based on carbon nucleophiles, such as the Suzuki, 27 Negishi, 28 Kumada, 29 and Sonogashira 30 reagents, require a transition metal catalyst for amide coupling via C–N bond activation to yield the corresponding ketones.…”

An efficient and straightforward approach for accessing thionoesters via palladium-catalyzed C–N cleavage of thioamides

“…Szostak, 40–57 Garg, 58–68 Zou, 69–71 Yamaguchi, 72–76 Huang, 77–83 Shi, 84–86 and Rueping 87–89 have made great contributions to the study of amide transformation. Our group 90–105 has also conducted excellent research in this field. As a thiocarbonyl analog of amide, it is extremely rarely reported that activated thioamide C–N bond cleavage formed various thio-compounds.…”