Fluorination of Secondary and Primary Alcohols by Thermal Decomposition of Electrochemically Generated Alkoxy Triphenylphosphonium Tetrafluoroborates
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概要
- 論文の詳細を見る
Replacement of hydroxyl groups in secondary and primary alcohols (1) with a fluorine atom arising from tetrafluorobote anion has been performed by the electrochemical formation of alkoxy triphenylphosphonium tetrafluoroborarates (2) from 1,followed by their thermal decomposition. The procedure is quite simple, involving : (1) constant-current electrolysis of a mixture of 1,Ph_3P, and Ph_3PH・BF_4 in CH_2Cl_2 in an undivided cell; (2) refluxing a tetrahydrofuran or dioxane solution of the residue afforded by evaporation of the solvent in vacuo after the electrolysis. Cyclic secondary alcohols such as 3β-hydroxy steroids and 2-adamantanol are transformed into the corresponding fluorides in satisfactory yields when the geometry of the leaving group in 2 is suitable for the substitution or an elimination process for 2 to give an alkene is stereochemically forbidden. The fluorination of steroidal alcohols and 4-phenyl-1-cyclohexanol proceeded with complete inversion, demonstrating that a fluorine atom from the tetrafluoroborate anion attacks from the side opposite to the phosphonium moiety in 2 via an SN2 mechanism rather than as SN1 mechanism. The fluorination of acyclic secondary and primary alcohols was performed by the present method in reasonable yields, although the reaction for the latter required more forcing conditions, such as refluxing in dioxane.
- 公益社団法人日本薬学会の論文
- 1996-08-15
著者
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OHMORI Hidenobu
Graduate School of Pharmaceutical Sciences, Osaka University
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MAEDA Hatsuo
Faculty of Pharmaceutical Sciences, Osaka University
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OHMORI Hidenobu
Faculty of Pharmaceutical Sciences, Osaka University
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Koide T
Faculty Of Pharmaceutical Sciences Osaka University
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Koide Takashi
Tokyo Research Laboratories Kowa Co. Ltd.
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Matsumoto Shun-ichiro
Institute For Drug Discovery Research Yamanouchi Pharmaceutical Co. Ltd.
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Maeda Hatsuo
Faculty Of Pharmaceutical Sciences Osaka University
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Matsumoto Sayaka
Faculty Of Pharmaceutical Sciences Osaka University
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Koide Takashi
Faculty Of Pharmaceutical Sciences Osaka University
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Ohmori H
Graduate School Of Pharmaceutical Sciences Osaka University
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Ohmori Hidenobu
Faculty Of Pharmaceutical Sciences Osaka University
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Koshi T
Tokyo Research Laboratories Kowa Co. Ltd.
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