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Organocatalytic sulfoxidation
Tetrahedron ( IF 2.1 ) Pub Date : 2020-11-24 , DOI: 10.1016/j.tet.2020.131784
Stuart C. Davidson , Gabriel dos Passos Gomes , Leah R. Kuhn , Igor V. Alabugin , Alan R. Kennedy , Nicholas C.O. Tomkinson

Treatment of a sulfide with a catalytic amount of a 1,3-diketone in the presence of silica sulfuric acid as a co-catalyst and hydrogen peroxide (50% aq) as the stoichiometric oxidant leads to the corresponding sulfoxide product. The reaction is effective for diaryl, aryl-alkyl and dialkyl sulfides and is tolerant of oxidisable and acid sensitive functional groups. Investigations have shown that the tris-peroxide 2, formed on reaction of pentane-2,4-dione with hydrogen peroxide under acidic reaction conditions, can oxidise two equivalents of sulfide using the exocyclic peroxide groups whereas the endocyclic peroxide remains intact. Calculations provide a mechanism consistent with experimental observations and suggest the reaction proceeds via an initial acid catalysed ring opening of a protonated tris-peroxide prior to oxygen transfer to a sulfur nucleophile.



中文翻译:

有机催化磺氧化

在二氧化硅硫酸作为助催化剂和过氧化氢(50%aq)作为化学计量氧化剂的存在下,用催化量的1,3-二酮处理硫化物,得到相应的亚砜产物。该反应对于二芳基,芳基烷基和二烷基硫化物是有效的,并且对可氧化的和酸敏感的官能团具有耐受性。研究表明,在酸性反应条件下,戊烷-2,4-二酮与过氧化氢反应生成的过氧化物2可使用环外过氧化物基团氧化两当量的硫化物,而环内过氧化物则保持完整。计算提供了与实验观察结果一致的机制,并表明反应通过氧转移到硫亲核试剂之前,质子化的过氧化物的初始酸催化开环。

更新日期:2020-12-17
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