氮杂小环硅醚催化剂的合成及其在不对称催化反应中的应用-有机化学专业论文.docx

摘要 摘要 近年来，氮杂小环有机催化剂由于其原料易得、合成方法简便、对环境友 好，已被广泛研究。如何设计、合成出具有高活性、高选择性的氮杂环有机小 分子催化剂已经成为当前研究的热点。 1 氮杂三、四环硅隧催化剂的合成 从三苯甲基氮杂三、四元环甲酸甲醋出发，经三步成功合成出一种新型氮 杂环硅酶催化剂。相关产物的结构通过核磁共振氧谱、核磁共振碳谱、质谱、 红外等手段进行了表征。 2 不对称 Michael 加成反应研究 将该催化剂用于脂肪醒 各类硝基烯怪的不对称 Michael 加成反应，系统 考察了反应溶剂、温度、时间等影响因素。 0.25 mmol 的硝基烯与 2.5 mmol 的 脏在 o .C或 28 .C下，以无水乙腊为溶剂，使用 10mol% 成 20mol%倍蠢的催 化剂，反应 48 h ，可获得最高达98%的 e.e.值。 3 不对称控股化反应研究 将此催化剂也用于各种醒与亚硝幕苯的 α挠版化反应， 1 mmol 的亚硝基苯 与 3 mmol 的醒在 o .C下，以无水二氯甲炕为溶剂，使用 20 mol%倍量的催化 剂，反应 1-2 h ，获得高达85%的 e.e.值。 关键词: 氮杂环旺酷 Michael 加成反应硝基烯 α-控股化反应亚硝基苯 Abstract Abstract Recent1y，smallring N-heterocyclic organocatalysts have been studied widely because of their facile material ，easily synthetic methods and environment而iend. How to design，synthesize small-molecule Nheterocyc1ic organocatalysts with high reactivity and excellent selectivity has been a research hotspot. 1The synthesis of small-ring N-heterocyclic silyl ethers catalysts Starting from (句-methyl azetidine-2-carboxylate or (功唰methyl aziridine-2- carboxylate，a novel N-heterocyclic silyl ether catalyst was successfully prepared via a three-step route. The structures of related products were characterized by lH NMR 、13CNMR、MS、IR. The application in asymmetric Michael addition recation 咀le Nheterocyclic silyl ether catalyst was used for the as泸nmetric Michael addition of various aliphatic aldehydes and different nitroolefins. Influential factors were s阳died in detail，such as temperature ，time and solvent. When 2.5 mmol aliphatic aldehydes and 0.25 mmol nitroolefins were st加ed with 10 mol% (or 20 mol%) catalysts in anhydrous acetonitrile at 0 C (or 28 .C) for 48 h，high enantioselectivity (98%) w町e achieved. The application in asymmetric Oxyamination recation ηle N-heterocyclic silyl ether catalyst also w部 used for the asymmetric αhydroxyamination recation of various aldehydes and nitrosobenzene. When aliphatic aldehydes and nitrosobenzene were stirred with 20 mol% catalysts in anhydrous dichloromethane