Hydrogenation of sulfoxides to sulfides mediated by incomplete cubane-type Mo3S4 clusters: synthetic applications and mechanistic insights†‡

IF 4.4 3区 化学 Q2 CHEMISTRY, PHYSICAL Catalysis Science & Technology Pub Date : 2024-10-17 DOI:10.1039/d4cy00987h
Juanjo Mateu-Campos , María Gutiérrez-Blanco , Eva Guillamón , Vicent S. Safont , Rosa Llusar
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Abstract

Homogeneous catalysts for the deoxygenation of sulfoxides to sulfides have not been widely explored. Herein, we report a green and efficient protocol for the catalytic hydrogenation of sulfoxides using an air-stable diamino Mo3S4 cluster complex under mild conditions (6 bar of H2 pressure and 50 °C in acetonitrile). Our strategy exhibits excellent group tolerance so it can be widely applied in the late-stage functionalization of pharmacological drugs and other valuable products containing sulfide moieties. Kinetic studies in combination with control experiments and DFT calculations support the operation of a sulfur-based cluster catalysis mechanism similar to the one previously reported for the hydrogenation of azobenzene and semihydrogenation of alkynes. What differentiates this mechanism from the analogous previous ones is that after hydrogen activation at two of the bridging sulfides to form an hydrosulfide intermediate, hydrogen is transferred sequentially first as a proton and then as a hydride.

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不完全立方体型 Mo3S4 团簇介导的硫氧化物加氢转化为硫化物:合成应用与机理研究†‡
将硫氧化物脱氧生成硫化物的均相催化剂尚未得到广泛探索。在此,我们报告了一种在温和条件下(6 巴 H2 压力和 50 °C乙腈)使用空气稳定的二氨基 Mo3S4 团簇配合物催化硫氧化物加氢的绿色高效方案。我们的策略具有出色的基团耐受性,因此可广泛应用于含有硫化物分子的药物和其他有价值产品的后期功能化。结合对照实验和 DFT 计算进行的动力学研究支持硫基簇催化机制的运行,该机制与之前报道的偶氮苯加氢和炔烃半加氢机制类似。该机制与之前类似机制的不同之处在于,氢在两个桥接硫化物上活化形成氢硫化物中间体后,氢首先以质子的形式,然后以氢化物的形式依次转移。
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来源期刊
Catalysis Science & Technology
Catalysis Science & Technology CHEMISTRY, PHYSICAL-
CiteScore
8.70
自引率
6.00%
发文量
587
审稿时长
1.5 months
期刊介绍: A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis. Editor-in-chief: Bert Weckhuysen Impact factor: 5.0 Time to first decision (peer reviewed only): 31 days
期刊最新文献
Back cover Back cover Characterizing Y224 conformational flexibility in FtmOx1-catalysis using 19F NMR spectroscopy. Lanthanum-doped nickel-based composite metal oxide catalyst for hydrogenation of isophthalonitrile to produce meta-xylenediamine† IBzH (IBenzhydryl): sterically-flexible N-aliphatic N-heterocyclic carbenes (NHCs) for iron-catalyzed C(sp3)–C(sp2) cross-coupling of unactivated haloalkanes†
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