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目的:创建共轭硝基烯与活性醛的不对称Morita-Baylis-Hillman(MBH)反应催化体系,筛选具有高催化活性及对映选择性的手性催化剂。方法:将21种手性有机小分子催化剂应用于β-硝基苯乙烯与乙醛酸乙酯的不对称MBH反应中,用手性高效液相色谱分析测定产物ee值,并考察温度、溶剂、底物比例等因素对催化反应的影响。结果:在金鸡纳生物碱类催化剂(DHQ)2AQN作用下,β-硝基苯乙烯与乙醛酸乙酯在甲苯中0℃下反应,获得光学纯度为56.9%ee的MBH加成产物,化学产率为60%。结论:以芳香基团作为桥联基的双金鸡纳生物碱类催化剂能够有效地催化β-硝基苯乙烯与乙醛酸乙酯的不对称MBH反应顺利进行,并获得中等程度的化学分离产率及对映选择性。
OBJECTIVE: To establish an asymmetric Morita-Baylis-Hillman (MBH) reaction catalyzed by conjugated nitroalkenes and reactive aldehydes to screen for chiral catalysts with high catalytic activity and enantioselectivity. Methods: 21 kinds of chiral organic small molecule catalysts were applied to the asymmetric MBH reaction of β-nitrostyrene and ethyl glyoxylate. The ee values of the products were determined by chiral high performance liquid chromatography. The effects of temperature, solvent , Substrate ratio and other factors on the catalytic reaction. Results: β-nitrostyrene reacted with ethyl glyoxylate in toluene at 0 ℃ under the action of cinchona alkaloid catalyst (DHQ) 2AQN to obtain the MBH addition product with optical purity of 56.9% ee. The chemical The yield is 60%. CONCLUSION: The birch cinnamon alkaloids with aromatic groups as bridging groups can effectively catalyze the asymmetric MBH reaction of β-nitrostyrene and ethyl glyoxylate with moderate degree of chemical separation Rate and enantioselectivity.