Development and application of fundamental chiral molecular tools

基础手性分子工具的开发与应用

基本信息

批准号：
19350048
负责人：
MURAI Toshiaki
金额：
$ 11.73万
依托单位：
Gifu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2007
资助国家：
日本
起止时间：
2007 至 2010
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-19350048/
关键词：
キラル分子ツールセレノリン酸塩化物セレノリン酸エステルセレノリン酸塩フッ素化加水分解セレリン酸クロリド絶対配置光学分割 BISEPCl 絶対配置決定ジアステレオマー混合物 31P NMR 77Se NMR BISEPCI

项目摘要

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.

已经开发了与脂肪族取代基的二级光学活性醇和光学活性循环胺合成的方法。作为关键起始材料，使用具有光学活性1,1'-2-二磷酸基团的磷酸苯烯酰基。氯化物与醇的反应顺利进行，以得到相应的酯。披露了酯的1^H，<13>^c，<13>^c，<31>^p和<77>^se nmr光谱，并根据这些值确定了次生醇的绝对构型的方法。酯与胺的反应是在附着在氧原子上的碳原子处的构型反转。借助这种特性，将源自二醇的酯与苄胺反应，以良好的产率导致2-烷基哌啶。将氯化物转化为磷酸硅氧酸及其盐。将酸测试为有机催化剂。在这些研究中，揭示了氟原子对磷原子的高亲和力。使用该特性，可以实现磷酸酯的荧光水解，从而使磷酸化的单植物具有高效率。