Organocatalytic sulfoxidation

TETRAHEDRON

卷:78

Article

Davidson, Stuart C.¹  Gomes, Gabriel dos Passos^2,3,4  Kuhn, Leah R.²  Alabugin, Igor, V²  Kennedy, Alan R.¹  Tomkinson, Nicholas C. O.¹ 

[1] Univ Strathclyde, Dept Pure & Appl Chem, WestCHEM, Thomas Graham Bldg,295 Cathedral St, Glasgow G1 1XL, Lanark, Scotland

[2] Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA

[3] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada

[4] Univ Toronto, Dept Comp Sci, 214 Coll St, Toronto, ON M5T 3A1, Canada

关键词: Peroxides;    Sulfoxidation;    DFT calculations;   

DOI  :  10.1016/j.tet.2020.131784

来源: Elsevier

【 摘 要 】

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.

【 授权许可】

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