Organocatalytic sulfoxidation
Organocatalytic sulfoxidation
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DOI：
10.1016/j.tet.2020.131784
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发表时间：
2021-01-08
期刊：
影响因子：
2.1
通讯作者：
Tomkinson, Nicholas C. O.
中科院分区：
文献类型：
--
作者：
Davidson, Stuart C.;Gomes, Gabriel dos Passos;Tomkinson, Nicholas C. O.
在硅硫酸作为助催化剂和过氧化氢（50%水溶液）作为化学计量氧化剂存在下，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醚有效，并且耐受可氧化和酸敏感的官能团。研究表明，戊烷-2,4-二酮与过氧化氢在酸性反应条件下反应形成的三过氧化物2可以利用环外过氧化物基团氧化两当量的硫化物，而环内过氧化物保持完整。计算提供了与实验观察一致的机制，并表明反应通过质子化三过氧化物的初始酸催化开环进行，然后氧转移到硫亲核试剂。 (C) 2020 Elsevier Ltd. 保留所有权利。
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. (C) 2020 Elsevier Ltd. All rights reserved.