Chemoselective Transition-Metal-Free Acylation of Thioamides by N–C(S) Bond Cleavage using Acyclic Twisted Thioamides

Abstract

A new method for chemoselective transition-metal-free acylation of thioamides with ketones by N–C(S) bond cleavage is reported. The approach exploits acyclic twisted thioamides to accomplish selective thio-Claisen condensation by ground state-destabilization of the thioamide bond. The valuable 3-hydroxy-1-thioxoketone products are obtained from bench-stable thioamide precursors under mild transition-metal-free, room temperature conditions. Various ground-state-destabilized thio-amides are amenable to this selective thio-acylation protocol. The method advances the reactivity of twisted thioamides to C–C bond forming reactions under transition-metal-free conditions.

Supplementary files

Article information

Article type
Research Article
Submitted
25 Dec 2024
Accepted
21 Feb 2025
First published
22 Feb 2025

Org. Chem. Front., 2025, Accepted Manuscript

Chemoselective Transition-Metal-Free Acylation of Thioamides by N–C(S) Bond Cleavage using Acyclic Twisted Thioamides

J. Zhang, Y. He, X. Zhu, Y. Guo, X. Wang, R. Wang and M. Szostak, Org. Chem. Front., 2025, Accepted Manuscript , DOI: 10.1039/D4QO02417F

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