Solvent-driven C(sp3)–H thiocarbonylation of benzylamine derivatives under catalyst-free conditions
- 4 January 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Green Chemistry
- Vol. 23 (2), 767-773
- https://doi.org/10.1039/d0gc03832f
Abstract
Due to the particularity of the thiocarbonyl group (CS bond), only limited C(sp3)–H thiocarbonylation methods, especially efficient and convenient methods, have been developed for the synthesis of thioamides. Inspired by the “solvent-specificity-based” design strategy, we discovered a simple, practical and environmentally friendly C(sp3)–H thiocarbonylation of benzylamine substrates for facile thioamide synthesis under catalyst-free conditions. A diverse array of benzylamine derivatives were tolerated by this catalyst-free thiocarbonylation. Furthermore, the (QM) computations and well-designed experiments on the reaction mechanism revealed that this thiocarbonylation depends on the specific solvent that initially drives this reaction through the intermolecular hydrogen atom transfer (HAT). And the following single electron transfer (SET) induces the electron-catalyzed C–S bond formation and intramolecular HAT realizing the final establishment of the CS bond.Funding Information
- National Natural Science Foundation of China (21702236, 81803436)
- Guangzhou Science, Technology and Innovation Commission (201805010005)
This publication has 61 references indexed in Scilit:
- The new world of organic reactions in waterPure and Applied Chemistry, 2013
- Recent advances in the Willgerodt–Kindler reactionChemical Society Reviews, 2013
- Intramolecular Direct Dehydrohalide Coupling Promoted by KOtBu: Total Synthesis of Amaryllidaceae Alkaloids Anhydrolycorinone and OxoassoanineOrganic Letters, 2012
- Silver(I)-Promoted Conversion of Thioamides to Amidines: Divergent Synthesis of a Key Series of Vancomycin Aglycon Residue 4 Amidines That Clarify Binding Behavior to Model LigandsJournal of the American Chemical Society, 2012
- Fluorescence Signaling of Zr4+by Hydrogen Peroxide Assisted Selective Desulfurization of ThioamideInorganic Chemistry, 2012
- Cell-Permeable and Plasma-Stable Peptidomimetic Inhibitors of the Postsynaptic Density-95/N-Methyl-d-Aspartate Receptor InteractionJournal of Medicinal Chemistry, 2011
- Closthioamide: An Unprecedented Polythioamide Antibiotic from the Strictly Anaerobic Bacterium Clostridium cellulolyticumAngewandte Chemie, 2010
- Reactions of C−H Bonds in WaterChemical Reviews, 2007
- Synthesis of ω-AminodithioestersSynthesis, 2006
- A Simple Method for the Synthesis of Thiobenzamides by Friedel-Crafts ReactionSynthesis, 1988