Cyclic dithiocarbonates of the type 1,3‐oxathiolane‐2‐thione were selectively and efficiently produced from the reaction between epoxides and CS2 using disodium bis‐benzimidazolate salts as catalysts. We have designed and synthesized three nucleophilic catalysts from the neutral forms of bis‐benzimidazole compounds (BBE‐Me, BBE‐H and BBE‐NO2), through simple procedures. All three catalysts, with aryl substituents possessing different electronic characteristics, were able to selectively catalyze the production of cyclic dithiocarbonates. BBE‐Me proved to be the most effective catalyst in the initial screening with 1,2‐epoxy‐3‐phenoxypropane, converting 95% of the epoxide with 99% of selectivity for the cyclic dithiocarbonate 1,3‐oxathiolane‐2‐thione. This catalyst was subsequently used to evaluate various reaction parameters and then several epoxides were selectively converted to the respective cyclic dithiocarbonates, under mild conditions, with a low catalyst loading, short reaction times, and in a solvent‐ and additive‐free system. A mechanistic proposal, supported by high‐resolution mass spectrometry, demonstrated for the first time that a nucleophilic catalyst in this system can simultaneously activate both CS2 and the epoxide molecule.

中文翻译：

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使用双苯并咪唑酸盐作为多功能催化剂选择性合成环状二硫代碳酸酯


使用双-苯并咪唑酸二钠作为催化剂，由环氧化物和 CS2 反应选择性且高效地生产 1,3-氧唑烷-2-硫酮型的环状二硫代碳酸酯。我们通过简单的程序从双苯并咪唑化合物的中性形式（BBE-Me、BBE-H 和 BBE-NO2）设计并合成了三种亲核催化剂。所有三种催化剂的芳基取代基具有不同的电子特性，都能够选择性催化环状二硫代碳酸酯的产生。BBE-Me 被证明是 1,2-环氧-3-苯氧基丙烷初始筛选中最有效的催化剂，可转化 95% 的环氧化物，对环状二硫代碳酸酯 1,3-氧代氮氧化物-2-硫酮具有 99% 的选择性。随后使用该催化剂评估各种反应参数，然后在温和的条件下，以低催化剂负载量、短反应时间以及无溶剂和无添加剂的体系，将几种环氧化物选择性地转化为相应的环状二硫代碳酸酯。由高分辨率质谱支持的机理提案首次证明该系统中的亲核催化剂可以同时激活 CS2 和环氧化物分子。