Optically Active Alkyl Phenyl Phosphoramidates : Preparation and Stereochemistry of Acid-catalyzed Alcoholysis

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概要

• 論文の詳細を見る

• Both enantiomers of methyl (or ethyl) phenyl phosphoramidate (8,13) were prepared from the corresponding diastereomeric amidates of L-phenylalanine ester (5,10), via a transaminative reaction involving the following sequence : N-chlorination, treatment with sodium methoxide, and mild acid-catalyzed hydrolysis of the resulting amino acetal (7,12). Stereochemical studies of H^+- and BF_3-catalyzed alcoholyses of 8 and 13 indicated that the nature of the acid catalyst had a profound effect on the steric course of the reaction. Complete stereospecificity observed in H^+ catalysis was ascribed to direct displacement with inversion of configuration at phosphorus (A-2 mechanism). On the other hand, BF_3 catalysis, which produced both inversion (70%) and retention product (30%), was explained in terms of (1) a pentacoordinate intermediate mechanism for retention product formation and (2) a dual mechanism, pentacoordinate intermediate and direct displacement A-2 mechanisms, for inversion product formation.

• 社団法人日本薬学会の論文
• 1979-07-25

著者

• 小泉 徹

  富山医科薬科大学薬学部薬化学

• 小泉 徹

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 小林 恵子

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• Koizumi T

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 吉井 英一

  Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University

• 吉井 英一

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 吉井 英一

  富山医科薬科大学薬学部

• Koizumi Toru

  Faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 小林 恵子

  Faculty Of Pharmaceutical Sciences Kanazawa University

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