含手性硫原子化合物主要包括手性亚磺酸酯、手性亚砜以及手性亚磺酰胺，其在生物医药以及不对称有机合成领域有着重要而广泛的应用。目前，硫原子手性中心的构建方法主要有手性醇诱导、不对称氧化、亚砜阴离子不对称芳基化及烷基化等。现有方法能够分别实现手性亚磺酸酯、手性亚砜以及手性亚磺酰胺的合成。然而，能同时实现含手性硫原子三种化合物集成式合成的方法还有待开发，这需要合成化学从原理和效率上的进一步突破。针对这一问题，本项目拟采取有机小分子催化磺酰基不对称重排的策略制备含手性硫原子的活性中间体，将其分别与醇、亲核性烷基试剂以及胺发生亲核取代反应以实现含手性硫原子化合物的集成式合成。催化不对称重排是构建手性中心最高效、最理想的方法之一，其在硫原子手性中心构建方面的研究还未见报道。本项目的研究将为有机小分子催化构建硫原子手性中心的方法学发展和含有手性硫原子的天然产物、药物和配体的合成提供新的途径。

Chiral organosulfur compounds with a stereogenic sulfur atom include sulfinates, chiral sulfoxides and chiral sulfonamides. They are prevalent in natural products, medicinal chemistry, and also widely used as chiral auxiliaries, chiral ligands, and organocatalysts in asymmetric synthesis. In general, the stereogenic sulfur center are constructed through asymmetric oxidation, chiral alcohol induction, asymmetric sulfinylation and asymmetric arylation of sulfenate anions. The existing methods can respectively achieve the synthesis of chiral sulfoxide, chiral sulfenamide and chiral sulfinate. However, to our knowledge, a collective method for synthesis of three kind of chiral organosulfur compounds with a stereogenic sulfur atom was rarely investigated. The development of such method requires further breakthroughs of synthetic chemistry. Accordingly, we aim to develop a method to realize collective synthesis of chiral organosulfur compounds with a stereogenic sulfur atom through organocatalytic asymmetric sulfonyl rearrangement reaction. First, the stereogenic sulfur atom center will be constructed through organocatalytic sulfonyl rearrangement, following with substitution reaction with nucleophiles such as alcohol, nucleophilic alkylation reagent and amine, to deliver chiral sulfinates, chiral sulfoxides and chiral sulfinamides in a collective manner. Furthermore, the mechanism of this asymmetric rearrangement reaction will be investigated through isotopic tracer method and on-line infrared analysis. This project will provide a new avenue to construct chiral sulfur stereogenic center and realize the collectively synthesis of chiral organosulfur compounds with a stereogenic sulfur atom, including natural products, drugs and chiral ligands.