不对称催化构筑硼手性化合物

手性化合物在生物医药、功能材料、化学合成等领域发挥着非常重要的作用，其中绝大多数手性化合物都是碳手性化合物。近年来，杂原子手性化合物也吸引了很多有机化学家们的关注和研究，例如硫手性化合物、磷手性化合物、硅手性化合物等。硼是另一个重要的主族元素，有机硼化合物在合成化学中发挥着举足轻重的作用。硼原子外围有三个价电子，通常是以sp²杂化的形式形成一个含有空p轨道的有机硼化合物。值得一提的是，当有胺、膦或NHC卡宾存在时，硼原子上的空p轨道容易接受这些路易斯碱的孤对电子形成四配位有机硼化合物。四配位有机硼化合物是四面体结构，当所连接的四个基团不同时，会形成相应的硼手性化合物。手性有机硼化合物作为试剂或者催化剂应用到合成化学中。由于硼手性化合物的立体构型不稳定，关于硼手性化合物的研究鲜有报道。目前已报道的硼手性化合物都是通过手性拆分以及手性源合成的方法获得的。本论文主要是发展了两种过渡金属催化的方法，高效、高对映选择性构筑硼手性化合物。主要内容如下：

针对硼手性化合物立体构型稳定性差的问题，以双炔取代的N,N π-共轭四配位有机硼化合物作为底物，利用不对称CuAAC反应在温和的反应条件下高效、高对映选择性实现了41例硼手性化合物的合成。根据单晶数据确定了其绝对构型。该反应底物范围广，除了简单的叠氮化合物，含有叠氮取代的生物活性分子也能够很好的兼容；所得到的硼手性化合物能够通过Sonogashira偶联，Glaser偶联，Crabbe反应以及[3+2]环加成反应得到相应的衍生化产物，立体专一性也能得到很好的保持。结合理论计算以及实验数据，发现产物的消旋能垒高达34.6 kcal/mol。随后，对部分产物的分子轨道、紫外-可见吸收光谱、荧光光谱、CD光谱和CPL进行了测试。N,C π-共轭四配位硼手性化合物相对于N,N π-共轭四配位硼手性化合物在紫外-可见吸收光谱以及荧光发射光谱发生了明显的蓝移。在圆偏振荧光光谱上，化合物(R)-III-20a的不对称因子（g_lum）为1.7ⅹ10^-4，而化合物(R)-III-21和(R)-III-22的不对称因子（g_lum）都为-3.4ⅹ10^-4。

氟化硼络合二吡咯甲烷（BODIPYs）作为一类典型的四配位硼化合物，通常作为染料分子被广泛应用于生物标记或者光动力治疗等领域。以双(二亚苄基丙酮)钯作为催化剂，基于TADDOL骨架的手性膦化合物作为配体，通过分子内碳氢键活化的策略对BODIPYs母核进行去对称化，以高达99%收率以及93%的对映体过量值得到多例硼手性BODIPYs。该反应具有较好的底物适用性，对于供电子基团甲基、甲氧基、胺基，以及吸电子基团氟、氯、三氟甲基都可以很好的兼容。通过实验数据得出模板产物的消旋化能垒高达36.0 kcal/mol。经过对反应条件的微调，也能得到含有七元环、八元环以及九元环的硼手性BODIPYs。通过单晶衍射确定了产物的绝对构型。随后，对所获得的硼手性BODIPYs的性质进行一系列的测试，包括分子轨道、紫外-可见吸收光谱、荧光光谱以及CD光谱等。测试结果显示六元环产物IV-8a和IV-11能够达到深红/近红外区，可以用于荧光成像。衍生化产物IV-11可以作为手性荧光探针分子实现对手性环己二胺的对映选择性识别，衡量对映选择性识别能力的ef值为1.95。

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