用于药物合成的酮和酰亚胺选择性氢化反应研究

具有光学活性的手性仲醇结构存在于许多天然产物、药物、香料、农药以及功能性材料中。不对称氢化前手性酮是手性醇现有合成方法中较为高效且原子经济的方法之一。自Noyori一代和二代催化体系发现以来，过渡金属催化的酮不对称氢化有了快速发展，许多高效的催化体系已经成功应用于手性中间体和手性药物的工业化生产中。早期酮的不对称氢化体系，主要是以钌催化剂为主，近十年，铱催化酮的不对称氢化反应因其高效和高选择性而备受化学家青睐。近几年，廉价金属（锰、铁、钴和镍等）的催化体系得到发展并在催化酮的不对称氢化反应中取得众多进展。然而现已发展的催化体系存在一些不足，如配体或催化剂较不稳定、合成步骤繁琐，或者催化剂负载量大、底物范围窄等。此外，一些酮类化合物，例如甲基乙基酮和二芳基酮等的高活性高对映选择性氢化仍未解决。因此发展易合成、底物适用性广和高活性高对映选择性的催化剂是十分必要的。

本文从具有特殊官能团的药物关键中间体的合成出发，开发了两类化合物的高效氢化体系；在过程中总结发现，合成新二茂铁基三齿配体仍具有研究价值，因此合成了一系列新二茂铁骨架的三齿配体，并探索了其在不对称氢化领域的应用，主要内容有：

以环状酰亚胺为底物，借助新合成的二茂铁骨架的手性三齿配体的铱络合物，在低催化剂负载下（S/C = 2 000），通过直接氢化的方法实现了23例ω-羟基内酰胺和23例ω-羟基酰胺化合物的高效制备，产物收率高达99%。本体系中的氢化反应模式（开环/不开环）可以通过配体结构的微小调节而改变，从而得到两种产物。该反应具有较好的官能团耐受性，对于N-芳基、杂芳基环和烷基取代的底物都具有很好的反应活性。此外，该反应体系可以实现ω-羟基内酰胺和ω-羟基酰胺的克级规模制备，反应的TON高达48 000。

以α-N-杂芳基酮为底物，借助Noyori二代催化剂，通过不对称氢化的方法实现了22例β-杂芳基氨基醇的高效制备，产物有高达98%的分离收率和 99%的ee值。该反应具有很好的官能团耐受性，对于含咪唑、三氮唑和四氮唑的底物都具有很好的对映选择性控制。同时，该反应也具有很好的化学选择性，当体系中含有碳碳双键时，可以专一地只氢化碳氧双键而保留碳碳双键。此外，该反应体系可以实现苯巴那酯和舍他康唑关键手性中间体的克级规模制备，反应的TON高达4 000，氢化反应产物经由一步反应即可得到苯巴那酯药物分子。

在前期研究工作的基础上，设计合成了一系列新型二茂铁骨架的三齿PNN配体和PNP配体。和传统的二茂铁骨架相比，新开发的二茂铁骨架含有稳定性高且酸性更强的胺片段和富电子的膦片段。这两类配体具有稳定性好、合成简便、结构容易调节和富电性等特点。PNN和PNP配体在铱催化的酮的不对称氢化反应中具有较大差别，PNN配体对于位阻较大酮的不对称氢化的对映选择性控制较好，产物ee值可达93%，PNP配体在苯乙酮的不对称氢化中可获得89% ee值。

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