高价碘化物/DMSO介导下含硫杂环化合物的合成新方法研究

“有机硫化学”和“高价碘化学”均是新物质创造科学研究的热点领域。开发使用价廉易得的硫源试剂来高效合成硫代杂环化合物的绿色环保路线一直是合成化学家不懈的追求。价廉易得、环境友好的DMSO虽然已被广泛应用于多种有机氧化反应中，但是很少被报道用作硫源在反应产物中引入具有潜在药理活性的甲硫基。本项目拟在前期初步研究结果的基础上，研究高价碘化物与DMSO产生的具有亲电活性的高活性中间体与各种取代类型的芳炔、芳基乙烯类底物的分子内环合/甲硫基化反应、与杂环化合物C-H官能团化/直接甲硫基化反应；研究相关产物进一步衍生化反应及具有潜在药理活性的杂环化合物或活性药物分子在高价碘化物/DMSO-d6作用下的氘代甲硫基化反应；研究上述反应的选择性，阐明反应机理。本项目致力于开发合成具有潜在药理活性的含硫杂环化合物的新策略、新方法，为“有机硫化学”、“高价碘化学”和“绿色化学”的发展贡献力量。

Both ‘Organosulfur Chemistry’ and ‘Hypervalent Iodine Chemistry’ are hot fields in the scientific research of creating new materials. It is the unremitting pursuit of synthetic chemists to develop green and environment-friendly routes for the efficient synthesis of sulfur-containing heterocyclic compounds. Although dimethyl sulfoxide (DMSO) which is inexpensive, readily available, and environment-friendly has been widely used in various types of organic oxidative reactions, it has rarely been reported as a ‘sulfur source’ to introduce the methylthio group, which possesses potential pharmacological activities into the reaction products. On the basis of our preliminary studies, this project intends to study the intramolecular cyclization/methylthiolation reaction of various substituted arynes and arylethylene substrates, and the direct C-H functionalization/methylthiolation of various heterocyclic compounds, through the electrophilic active intermediate produced by hypervalent iodine oxidant and DMSO; to study the further derivatization reaction of related products, and the deuteromethylthiolation reaction of heterocyclic compounds or active drug molecules with potential pharmacological activity under the action of hypervalent iodine oxidant and DMSO-d6; to study the selectivity of the above reaction and clarify the reaction mechanism. The project is dedicated to developing a class of new strategy and a series of methods for synthesis of various types of S-containing heterocyclic compounds with potential pharmacological activities, making contribution to the development of ‘Organosulfur Chemistry’, ‘Hypervalent Iodine Chemistry’ and ‘Green Chemistry’.