Parikh Anuvasita, Parikh Parmeshthi, Kumar Madduluri Vimal, Sah Ajay K
Department of Chemistry, Birla Institute of Technology and Science, Pilani, Pilani Campus, Rajasthan, 333031, India.
Chem Asian J. 2025 Feb 17;20(4):e202401336. doi: 10.1002/asia.202401336. Epub 2025 Jan 4.
A combination of dinuclear molybdenum complex of bis-(4,6-O-ethylidene-β-D-glucopyranosylamine)-1,4-dihydroxy-2,5-dibenzylidene with urea hydrogen peroxide (UHP) has been used as an efficient catalyst for the selective oxidation of thiols into corresponding uronium sulfonate salts (UrR/ArSO₃). The reaction was carried out in ethanol at room temperature using sixteen different aliphatic and aromatic thiols, which afforded an excellent isolated yield of products (89-98 %). We have established the evolution of hydrogen gas during the oxidation process by gas chromatography, however no such reports are available for similar reactions in the past. The products have been characterized by several analytical techniques like FTIR, NMR, HRMS, etc., and the molecular structure of two compounds has been established by single crystal X-ray diffraction studies. The mechanistic insights of the catalytic process have also been explored, and during this process, the formation of disulfides, sulfinothioates, and sulfinic acids has been noticed. Two representative reactions have also been reported where (i) uronium p-chlorobenzene sulfonate has been converted to corresponding sulfonic acid and (ii) diphenyl diselenide has been oxidized to corresponding selenonate salt.
双-(4,6-O-亚乙基-β-D-吡喃葡萄糖胺)-1,4-二羟基-2,5-二亚苄基双核钼配合物与过氧化脲（UHP）的组合已被用作一种高效催化剂，用于将硫醇选择性氧化为相应的锍鎓磺酸盐（UrR/ArSO₃）。该反应在乙醇中于室温下进行，使用了16种不同的脂肪族和芳香族硫醇，产物的分离产率极高（89 - 98%）。我们通过气相色谱法确定了氧化过程中氢气的生成情况，然而过去没有关于类似反应的此类报道。产物已通过多种分析技术进行了表征，如傅里叶变换红外光谱（FTIR）、核磁共振（NMR）、高分辨质谱（HRMS）等，并且通过单晶X射线衍射研究确定了两种化合物的分子结构。还探索了催化反应的机理，在此过程中，注意到了二硫化物、亚磺硫酯和亚磺酸的形成。还报道了两个代表性反应，其中（i）对氯苯磺酸锍鎓已转化为相应的磺酸，（ii）二苯基二硒化物已被氧化为相应的硒酸盐。
