Thioesters play important roles in chemistry and biology, but their synthesis generally exhibits a poor atom economy and generates copious waste. We report here the dehydrogenative coupling of alcohols and thiols to yield thioesters and evolve H₂. This waste-free reaction is catalysed by an acridine-based ruthenium pincer complex in hexamethyldisiloxane as the optimal solvent without any additives. Various thioesters were formed in good-to-excellent yields using equivalent amounts of alcohols and thiols in excellent selectivity with hydrogen gas as the only by-product. A plausible mechanism, which involves an outer-sphere dehydrogenation process in which the thiol not only serves as a reactant, but also as an assisting ligand, is proposed based on mechanistic studies and the isolation of intermediates. This system provides a facile, efficient and waste-free synthesis of thioesters.

硫酸酯在化学和生物学中起着重要的作用，但是它们的合成通常表现出较差的原子经济性并产生大量废物。我们在这里报告了醇和硫醇的脱氢偶联反应，从而生成硫酯并释放出H ₂。这种无浪费的反应是由六甲基二硅氧烷中的as啶基钌钳配合物作为最佳溶剂而无任何添加剂而催化的。使用等量的醇和硫醇以极好的选择性将氢气作为唯一的副产物，从而以良好至优异的产率形成了各种硫酯。基于机理研究和中间体的分离，提出了一种可行的机理，其中涉及一个外球脱氢过程，其中硫醇不仅充当反应物，而且充当辅助配体。该系统提供了简便，高效且无浪费的硫代酯合成方法。