Development and application of fundamental chiral molecular tools

发展了识别具有脂肪族取代基的二次光学活性醇和合成光学活性环胺的方法。作为关键的起始原料，使用了具有光学活性的1，1‘-2-联萘基的磷硒酰氯。氯化物与醇的反应进行得很顺利，得到相应的酯。揭示了这些酯类化合物的1H，~lt；13&~C，~31&gt；^P和~lt；77&gt；^Se核磁共振谱的总体趋势，并在此基础上建立了确定仲醇绝对构型的方法。酯与胺的反应是在与氧原子相连的碳原子上的构型反转进行的。利用这一性质，将二元醇衍生的酯与苯甲胺反应生成2-烷基哌啶，产率较高。氯化物被转化为亚磷酸及其盐类。这些酸作为有机催化剂进行了测试。在这些研究中，氟原子对磷原子的高亲和力被揭示出来。利用这一性质，实现了磷酸酯的氟化水解，得到了高效的磷氟酸酯单酯。

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.