Solvent-Driven C(sp3)‒H Thiocarbonylation of Benzylamine Derivatives under Catalyst-Free Conditions
Solvent-Driven C(sp3)‒H Thiocarbonylation of Benzylamine Derivatives under Catalyst-Free Conditions
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无催化剂条件下溶剂驱动的苯甲胺衍生物 C(sp3)–H 硫代羰基化反应
DOI：
10.1039/d0gc03832f
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发表时间：
2021
期刊：
影响因子：
9.8
通讯作者：
wentao wei
中科院分区：
文献类型：
--
作者：
jingwei zhou;songping wang;yaoming lu;lamei li;wentao duan;qi wang;hong wang;wentao wei
由于硫代羰基（CS键）的特殊性，目前仅发展了有限的C（sp3）-H硫代羰基化方法，尤其是高效简便的方法。受"基于溶剂特异性"设计策略的启发，我们发现了一种简单、实用、环境友好的苄胺底物C（sp3）-H硫代羰基化反应，在无催化剂条件下合成硫代酰胺。各种各样的苄胺衍生物的耐受这种无催化剂的硫代羰基化。此外，（QM）的计算和精心设计的实验反应机理表明，这种硫代羰基化取决于特定的溶剂，最初驱动该反应通过分子间氢原子转移（HAT）。随后的单电子转移（SET）导致电子催化的C-S键形成和分子内HAT，最终实现CS键的建立。
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.