Development and application of fundamental chiral molecular tools

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Methods for the discrimination of secondary optically active alcohols with aliphatic substituents and for the synthesis of optically active cyclic amines have been developed. As a key starting material, phosphoroselenoyl chloride with optically active 1,1'-2-binaphthyl groups are used. The reaction of the chlorides with alcohols proceeded smoothly to give the corresponding esters. The general tendency of the 1^H, <13>^C, <31>^P, and <77>^Se NMR spectra of the esters was disclosed, and on the basis of these values, the method for the determination of the absolute configuration of secondary alcohols was established. The reaction of esters with amines proceeds with the inversion of the configuration at the carbon atom attached to the oxygen atom. With this properties, the ester derived from a diol was reacted with benzylamine to leads to 2-alkylpiperidine in good yield. The chloride was converted to phosphoroselenoic acids and their salts. The acids were tested as organocatalysts. During these studies, the high affinity of the fluorine atom toward the phosphorus atom was revealed. With this property, the fluoridative hydrolysis of phosphoric acid esters was achieved to give phosphorofluoridate monoesters with high efficiency.