新型手性胍和胍盐的分解及其在不对称Michael反应中的应用.pdfVIP

THE SYNTHESIS OF CHIRAL GUANIDINES AND GUANIDINIUM SALTS AND THEIR APPLOCATION IN ASYMMETRIC MICHAEL REACTIONS A Dissertation Submitted to the Graduate School of Henan University in Partial Fulfillment of the Requirements for the Degree of Master of Science By LiXin Li Supervisor: Prof. Jiang Zhiyong June, 2013 III 摘 要 胍基是精氨酸的侧链，以胍盐的形式存在，它同时也存在于许多天然产物。胍基可 以和许多含氧负离子如羰基和磷酸根等形成很强的离子对形式，而这些含氧负离子也存 在与酶和抗体中。在过去的几十年中，随着对有机化学研究的不断深入，不同的手性胍， 特别是轴手性胍和C -对称性的双环胍，已经被设计合成出，尤其是手性胍在不对称合 2 成中的卓越的催化能力，关于手性胍的高pKa 值和双氢键催化机理都得到了极大的关注 和发展。 在本论文中，我们第一次报道了手性双环胍催化的3-苄基取代的氧化吲哚和马来酰 亚胺的不对称Michael 加成，并取得了高非对应体比例和高对映体差的Michael 加成产 物。包含有季碳-叔碳相邻手性中心的几十个 3,3-二取代氧化吲哚的产物已经获得。这 也是第一例有关把 N-苄基α-支链的琥珀酰亚胺立体定向的引入到 3,3-二取代的氧化 吲哚分子中的报道。 关键词：不对称催化，有机催化，手性胍，吲哚酮，马来酰亚胺。 IV ABSTRACT The side chain of the amino acid arginine is guanidinium, and this moiety can also present in many natural products. The guanidinium group can generate strong ion-pairs with oxoanions such as carboxylates or phosphates in enzymes and antibodies. As the extension of this mechanism in organic chemistry, in the past few decades, various chiral guanidines, particularly the axially chiral guanidines and the C -symmetric bicyclic guanidines, have been designed and synthesized, and their high pKa values and 2 dual hydrogen-bonding modes have promoted an ever-increasing interest in asymmetric reactions. In this thesis, we have developed the first highly diastereo- and enantioselective Michael additions of 3-benzyl-substituted oxindoles to N-maleimides catalyzed by a C -symmetric bicyclic