Guo Yu, Lin Guotao, Zhang Mengjie, Xu Jian, Song Qiuling
Institute of Next Generation Matter Transformation, College of Material Sciences Engineering, Huaqiao University, Xiamen, 361021, Fujian, China.
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, 350108, China.
Nat Commun. 2024 Aug 25;15(1):7313. doi: 10.1038/s41467-024-51334-5.
Due to the high reactivity and versatility of benzenesulfonothioates, significant advancements have been made in constructing C-S bonds. However, there are certain limitations in the synthesis of S-thiosulfonates and SS-thiosulfonates, especially when dealing with substantial steric hindrance, which poses a significant challenge. Herein, we present an innovative approach for assembling unsymmetric S-thiosulfonates and unsymmetric SS-thiosulfonates through the integration of dual copper/photoredox catalysis. Moreover, we also realized the one-pot strategy by directly using carboxylic acids as raw materials by in-situ activation of them to access S-thiosulfonates and SS-thiosulfonates without further purification and presynthesis of NHPI esters. The envisaged synthesis and utilization of these reagents are poised to pioneer an innovative pathway for fabricating a versatile spectrum of mono-, di-, and polysulfide compounds. Furthermore, they introduce a class of potent sulfenylating reagents, empowering the synthesis of intricate unsymmetrical disulfides that were previously challenging to access.
由于苯磺硫酯具有高反应活性和多功能性，在构建碳-硫键方面已取得了重大进展。然而，在合成S-硫代磺酸酯和SS-硫代磺酸酯时存在一定限制，尤其是在处理较大的空间位阻时，这构成了重大挑战。在此，我们提出了一种通过双铜/光氧化还原催化相结合来组装不对称S-硫代磺酸酯和不对称SS-硫代磺酸酯的创新方法。此外，我们还通过直接使用羧酸作为原料，通过原位活化它们来实现一锅法策略，从而无需进一步纯化和预合成NHPI酯即可获得S-硫代磺酸酯和SS-硫代磺酸酯。这些试剂的设想合成和应用有望开创一条创新途径，用于制备多种单硫化物、二硫化物和多硫化物化合物。此外，它们还引入了一类有效的亚磺酰化试剂，使以前难以获得的复杂不对称二硫化物的合成成为可能。
