Heterogeneous asymmetric hydrogenation of quinolines for the production of optically active tetrahydroquinoline derivatives still remains a difficult task due to the aromatic stability of quinolines. Herein, we reported efficient heterogeneous asymmetric hydrogenation of quinolines over chiral porous polymers integrated with both chiral active sites (VDPEN-RuOTs) and substrate activation sites (TsOH). The porous polymer integrated with TsOH is 10 times more active than that without TsOH in the asymmetric hydrogenation of 2-methylquinoline. The volcano curve of TOF with the TsOH/Ru ratio confirms the synergistic catalysis of VDPEN-RuOTs and TsOH. Comparison results with a homogeneous catalytic system imply that the synergy between chiral centers and acidic sites is greatly enhanced in the polymer network. Under optimized conditions, the chiral porous polymer afforded up to 90% ee with 90 h^–1 TOF, which is one of the best solid catalysts for asymmetric hydrogenation of quinoline derivatives ever reported. Furthermore, the bifunctional porous polymers realized the asymmetric cascade hydrogenation/reductive amination reaction to obtain benzo-quinolizidines. Our primary results suggest that the incorporation of substrate activation sites near chiral centers is an efficient strategy for the synthesis of high-performance solid catalysts for heterogeneous asymmetric catalysis.

中文翻译：

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在手性多孔聚合物上与基质活化位点结合的喹啉的高效不对称加氢

由于喹啉的芳族稳定性，用于生产旋光四氢喹啉衍生物的喹啉的非均相不对称氢化仍然是一项艰巨的任务。在这里，我们报道了在与手性活性位点（VDPEN-RuOTs）和底物激活位点（TsOH）集成在一起的手性多孔聚合物上，喹啉的高效异质不对称氢化。在2-甲基喹啉的不对称氢化中，与TsOH结合的多孔聚合物的活性是没有TsOH的多孔聚合物的10倍。具有TsOH / Ru比的TOF火山曲线证实了VDPEN-RuOTs和TsOH的协同催化作用。与均相催化体系的比较结果表明，在聚合物网络中，手性中心与酸性位点之间的协同作用大大增强。在优化条件下，^–1 TOF，是迄今为止报道的喹啉衍生物不对称加氢的最佳固体催化剂之一。此外，双功能多孔聚合物实现了不对称的级联加氢/还原胺化反应，从而获得了苯并喹喔啉类。我们的主要结果表明，在手性中心附近结合底物活化位点是合成用于非均相不对称催化的高性能固体催化剂的有效策略。