Stereoselective Formation of Allylic Sulfides via Two Sequential[3,3]-Sigmatropic Rearrangements of Allylic Xanthates and Its Mechanistic Aspects

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概要

• 論文の詳細を見る

• O-(2-Alkynyl) S-alkyl dithiocarbonates (allylic xanthates) were pyrolyzed to give 2-alkenyl alkyl sulfides (allylic sulfides) via the corresponding allylically isomeric S-(2-alkenyl) S-alkyl dithiocarbonates. The reaction follows the first-order rate law with relatively low sensitivity to the ionizing power of the medium and sizeably negative entropies of activation. When a mixture of two dithiol esters having different S-(2-alkenyl) groups and different S-alkyl groups was pyrolyzed, a "cross product" was not observed. The reaction was found to be facilitated by the presence of phenolic compounds or Lewis acids.Based on these findings together with modified neglect of diatomic overlap (MNDO) calculation data, the mechanism for the formation reaction of 2-alkenyl alkyl sulfides is discussed.

• 公益社団法人日本薬学会の論文
• 1990-03-25

著者

• 原野 一誠

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 久野 拓造

  Faculty Of Pharmaceutical Sciences Kumamoto University

• 原野 一誠

  熊本大学 薬

• 原野 一誠

  熊本大学薬学部

• 久野 拓三

  熊本大学薬学部

• 山城 茂

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 三坂 恵祐

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 大泉 憲秀

  Faculty of Pharmaceutical Sciences, Kumamoto University

• 三坂 恵祐

  Faculty Of Pharmaceutical Sciences Kumamoto University

• 山城 茂

  Faculty Of Pharmaceutical Sciences Kumamoto University

• 大泉 憲秀

  Faculty Of Pharmaceutical Sciences Kumamoto University

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