Further Studies on the Oxy-functionalization of Cholesteryl Acetate with tert-Butyl Hydroperoxide and Tris (acetylacetonato) iron (III)

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概要

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• The time courses of the spectral change, decomposition, and consumption of Fe (acac)_3,tert-butyl (^τBu) hydroperoxide, and cholesteryl acetate, respectively, in the title reaction were followed and the reaction was inferred to be initiated by the active species originating from the interaction of the ferric chelate and the hydroperoxide. Radical processes seem to participate in this reaction, since it was completely inhibited by a radical scavenger (BHT), which was also effective in blocking the further transformation of the intermediary C (7)-^τBu-peroxide. The ^τBuBr-KO_2 system generating ^τBuOO radicals oxidized cholesteryl methylether almost exclusively to an epoxide. The ^τBuOOH-KO_2 system generating ^τBuO radicals, on the other hand, abstracted the allylic C (7)-hydrogen to give the ^τBu-peroxide, the alcohol, and the ketone, but no epoxide. The intermediary ^τBu-peroxide was assumed to be produced also by the nucleophilic attack of ^τBuOOH on the allylic cation, to which the initially formed C (7)-radical species was further oxidized. A proposed mechanism is presented for the title reaction.

• 公益社団法人日本薬学会の論文
• 1981-07-25

著者

• 武藤 俊樹

  Faculty of Pharmaceutical Sciences, Hokkaido University

• 武藤 俊樹

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 木村 通也

  Faculty Of Pharmaceutical Sciences Hokkaido University

関連論文

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• On the Mode of Epoxidation by the Tetraphenylporphinatoiron (III)-Iodosylbenzene System
• Iron-catalyzed Autoxidation of Liposomal Cholesterol
• On the Mode of Oxygenation with the Ferric Perchlorate-Hydrogen Peroxide System
• Iron-catalyzed Autoxidation of Cholesterol in the Presence of Unsaturated Long-chain Fatty Acid
• The Reactions of Cholesteryl Acetate with tert-Butyl Hydroperoxide and Molybdenum Complexes
• The Reactions of Cholesteryl Acetate with Various Hydroperoxides in the Presence of Tris (acetylacetonato) iron (III) and Hexacarbonylmolybdenum
• On the Reaction of Cholesteryl Acetate with tert-Butyl Hydroperoxide in the Presence of Tris (acetylacetonato) iron (III)
• Further Studies on the Oxy-functionalization of Cholesteryl Acetate with tert-Butyl Hydroperoxide and Tris (acetylacetonato) iron (III)

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