开环和C(ω)-S偶联：镍介导的脂环烷氧氢过氧化物转化

IF 2.5 3区化学 Q2 CHEMISTRY, ORGANIC

European Journal of Organic Chemistry Pub Date : 2025-02-17 DOI:10.1002/ejoc.202401198

Dmitri I. Fomenkov , Roman A. Budekhin , Olga M. Mulina , Olga A. Komarova , Mikhail M. Doronin , Yulia Yu. Belyakova , Liang‐Nian He , Ivan A. Yaremenko , Alexander O. Terent'ev

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引用次数: 0

摘要

在含醇溶液中臭氧分解环烷酮缩氨基酮，随后加入镍（II）二硫代氨基甲酸酯或黄原酸酯，得到ω-黄原酸酯或ω-二硫代氨基甲酸酯。反应分几个步骤进行。第一个是环烷酮缩氨基脲在醇的存在下臭氧分解，生成脂环烷氧双氧水。第二步是烷氧氢过氧化物与二硫代氨基甲酸镍或黄药之间的特殊相互作用，通过烷氧基自由基的形成和随后的β-裂解，产生C-S偶联产物。所开发的方法可以得到ω-黄酮或ω-二硫代氨基酯，相对于最初的环烷酮缩氨基酮，收率高达52%。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Ring Opening and C(ω)‐S Coupling: Nickel‐Mediated Transformation of Alicyclic Alkoxyhydroperoxides

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Ring Opening and C(ω)‐S Coupling: Nickel‐Mediated Transformation of Alicyclic Alkoxyhydroperoxides

Ozonolysis of cycloalkanone semicarbazones in alcohol containing solution with the subsequent addition of nickel (II) dithiocarbamates or xanthates was found to result in ω‐xanthyl or ω‐dithiocarbamyl carboxylic acid esters. The reaction proceeds in several steps. The initial one is cycloalkanone semicarbazone ozonolysis in the presence of alcohol, which leads to alicyclic alkoxyhydroperoxide. The second step is an extraordinary interaction between the alkoxyhydroperoxide and nickel (II) dithiocarbamate or xanthate, which proceeds via alkoxy radical formation and its subsequent β‐scission, resulting in C−S coupling products. The developed method allows to obtain ω‐xanthyl or ω‐dithiocarbamyl esters in yields up to 52 % relative to the initial cycloalkanone semicarbazone.

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来源期刊

European Journal of Organic Chemistry 化学-有机化学

CiteScore

5.40

自引率

3.60%

发文量

752

审稿时长

1 months

期刊介绍： The European Journal of Organic Chemistry (2019 ISI Impact Factor 2.889) publishes Full Papers, Communications, and Minireviews from the entire spectrum of synthetic organic, bioorganic and physical-organic chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form two leading journals, the European Journal of Organic Chemistry and the European Journal of Inorganic Chemistry: Liebigs Annalen Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry.