Study on Electron Transfer Reaction on Electrode aimed at Nitrogen Atomcontaining Pharmaceuticals

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We have studied in detail on the electron transfer reactions from carbamates to electrode in order to efficiently apply the electochemical reactions to fine organic synthesis which involves nitrogenatom containing pharmaceuticals. The following results were obtained.1) Electorhchemical oxidation of proline ester and asymmetric synthesis : Electrochemical oxidation of N-methoxycarbonylated proline ester in methanol was carried out to see the regioselectivity, that is, selectivity of the oxidation at alpha-and alpha'-positions, and optically active alpha-alkylprolines were prepared by use of the oxidation products.2) beta-Substituent effect on electron transfer reaction : Electrochemical oxidation of carbamates possessing a halogen atom or a methoxycarbonyl group at the beta-position was investigated in order to clarify the substituent effect on the electron transfer reaction, and it was found that such electron-withdrawing substituents did not give much effect on the electron transfer type oxidation. As the results, a-substituted aziridines could be synthesized utilizing the oxidation products.3) Introduction of substituent on gamma-position of piperidine ring : Asymmetric introduction of an alkyl group into the gamma-position of piperidine ring was achieved by use of the electrochemical oxidation products of N-methoxycarbonylpiperidine.4) Application to fine organic synthesis : The following three projects, i) diastereoselective synthesis of 3-amino-2-hydroxyalkanecarboxylic acids using electrochemical oxidation products, ii) synthesis of enamines possessing a variety of functional groups from primary amines, and iii) preparation of optically active beta-hydroxyamines from primary amines, were achieved.