节点文献
不对称有机催化反应研究
Research on Asymmetric Organocatalysis
【作者】 杨进；
【导师】 张雅文；
【作者基本信息】 苏州大学 ， 有机化学， 2009， 硕士
【摘要】 第一部分:有机分子催化的高选择性Aldol反应实现的动态动力学拆分有机分子催化的,丙酮对β-取代的α-酮酯的Aldol反应,能够通过动态动力学拆分的进程,以较高的产率,优秀的非对映选择性(dr达到99:1)和对映选择性(ee达到98%),获得单一的异构体。反应产物的绝对构型通过X-衍射分析确定。反应经过的动态动力学拆分通过一个可能的过渡态进程进行了描述。第二部分:新型双官能团催化剂的设计合成及在Michael加成中的应用初探依据分子识别的概念,设计合成一种新型双官能团催化剂。该催化剂从L-脯氨酸出发,保留四氢吡咯环结构,使用吡啶胺的骨架,通过添加质子酸从而以双氢键对硝基结构产生识别。该催化剂对环己酮和硝基烯的Michael加成具有很好的选择性。
【Abstract】 Part 1: Highly Diastereo- and Enantioselective Organocatalytic Addition of Acetone toβ-Substitutedα-Ketoesters via Dynamic Kinetic ResolutionThe L-proline catalyzed aldol reactions ofβ-substitutedα-ketoester with acetone proceeded with dynamic kinetic resolution and gave a single diastereoisomer in good yield with excellent diastereoselectivity (dr up to >99:1) and enantioselectivity (ee up to 98%). The absolute configuration of the chiral adduct was assigned by a single crystal X-ray diffraction analysis. A tentativel reaction mechanism was briefly discussed.Part 2: Design of Tunable Bifunctional Organocatalyst Based on Molecular Recognition and its application in Asymmetric Michael Addition Reaction of Ketones to NitroolefinsA new catalyst was designed based on molecular recognition. Its application in asymmetry Michael addition reaction was investigated. The possible dual activation model was proposed.