Synthesis ( IF 2.6 ) Pub Date : 2020-06-22 , DOI: 10.1055/s-0040-1707104 Sylwia Sowa 1 , Kamil Modzelewski
Abstract
A new alkylation protocol for the synthesis of tertiary phosphonite/phosphinite-boranes is developed. P-Alkylation products are obtained exclusively in moderate to very good yields from easily accessible (1-hydroxy-1-methylethyl)/(1-hydroxy-1-cyclohexyl) phosphonite/phosphinite-boranes upon reaction with a variety of electrophiles under mild conditions. The methodology opens up new synthetic routes for organophosphorus chemistry and offers access to valuable alkyl phosphonite/phosphinite-boranes. In contrast to previously reported oxidative removal–substitution sequences for the preparation of optically active phosphinite-boranes, our protocol provides a one-step procedure that occurs without loss of stereochemical information at phosphorus. This new approach provides a rather advantageous protocol when compared to direct alkylation methods (which may undergo P-epimerization) and occurs in a stereoselective manner even at 0 °C.
中文翻译:
通过PH键的临时保护进行亚膦酸酯/亚膦酸酯-硼烷的烷基化
摘要
开发了用于合成亚膦酸酯/次膦酸酯-硼烷的新的烷基化方案。在温和的条件下与各种亲电试剂反应后,容易获得的(1-羟基-1-甲基乙基)/(1-羟基-1-环己基)亚膦酸酯/次膦酸酯-硼烷仅以中等至非常高的产率获得P-烷基化产物。该方法为有机磷化学开辟了新的合成途径,并提供了获得有价值的烷基亚膦酸酯/次膦酸酯-硼烷的途径。与先前报道的用于制备旋光性次膦酸酯-硼烷的氧化去除-取代序列相反,我们的方案提供了一步操作,并且不会丢失磷处的立体化学信息。