钌催化烯丙基醇的动力学拆分以及二苯基 氯化膦还原的机理研究

手性烯丙基醇结构存在于许多药物分子和生物活性分子当中，是天然 化合物最重要的结构单元之一。目前，对于该结构的合成方法主要是在金 属或有机催化剂的存在下对羰基化合物进行对映选择性加氢，然而该方法 对于某些底物存在一定局限性。另一方面，动力学拆分能够提供与不对称 氢化绝对构型相反的手性烯丙醇，可以与氢化法形成互补。本文报道了一 种手性钌（II）氢转移催化剂，可以对一类含有（Z）-烯烃基团的烯丙醇 底物进行有效的动力学拆分以构建对应的手性（Z）-烯丙醇，其拆分效率 （s 值）位于第一梯队。该方法还能有效应用于含有 Z/E 混合物的外消旋烯 丙醇的动力学拆分，以产生只含纯（Z）-烯丙醇的产物。 为了探究该方法对于生物活性分子的合成应用，查阅文献设计了使用 该方法合成 1,2-胺基醇缩酮（生物活性分子）的合成路线，并进行了外消 旋产物的合成。使用该修饰后的方法合成了相应的 1,2-胺基醇并进行了表 征。 对三价膦氯化物进行转化是工业上合成各种三价膦衍生物的最重要方 法，而二苯基膦作为一种非常重要的化工原料，其合成需要使用无机强还 原剂进行反应。本文报道了一种使用甲酸盐进行二苯基氯化膦还原的例子， 并通过理论计算解析了其反应过程，阐明了其目前产率存在上限的原因， 同时提出了进一步提高产率的办法。

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