【作者】 胡袁春；

【导师】 梁鑫淼；

【作者基本信息】 中国科学院研究生院（大连化学物理研究所） ， 有机化学， 2003， 博士

【摘要】 本文从手性NOBIN和手性BINOL出发，设计、合成了一类新型的亚磷酸酯-吡啶配体，并系统地研究了它们在铜（Ⅰ）催化Et₂Zn对α，β-不饱和烯酮的1，4-共轭加成反应中的应用。结果表明：（S）-NOBIN和（S）-BINOL衍生的配体是匹配的，其中BINOL部分的手性对产物的绝对构型起主导作用；配体中吡啶氮参与了与Cu（Ⅰ）的配位，吡啶 6-位的甲基取代基对反应具有明显的影响。配体（S，S）-La对亚苄基丙酮类底物具有较好的手性诱导能力。配体（S，S）-Lc则对取代查耳酮底物表现出更高的对映体选择性，最高ee值达到97.1％，是目前这一反应体系的最好结果之一。 通过对联萘骨架进行部分加氢开发出一类型的H₈-联萘亚磷酸酯-吡啶配体Lk-Lp，它们在Cu（Ⅰ）-催化Et₂Zn对烯酮的1，4-共轭加成反应中的应用表明：（S）-H₈-NOBIN和（S）-BINOL衍生的配体（S,S）-Ll对各种取代查耳酮都取得了很好的ee值；相应的配体（S,S）-Lk则对取代亚苄基丙酮底物表现出很高的手性诱导能力，最高ee值达到97.8％，是目前这一反应体系的最好结果。 配体LA的光学纯度与1，4-共轭加成产物的ee值间呈现明显的正的非线性效应。实验数据符合Kagan的ML₂模型。 在亚磷酸酯-吡啶配体-Cu（Ⅰ）络合物催化的Et₂Zn对烯酮的1，4-共轭加成反应中，观察到随着反应温度的提高加成产物的绝对构型发生了反转。更多还原

【Abstract】 A new type of phosphite-pyridine ligands derived from chifal NOBESJ and BINOL were designed, synthesized and employed in Cu(I)-catalyzed enantioselective 1,4-conjugate addition of EtiZn to enones. The results demonstrated that the ligands derived from (S)-NOBIN and (S)-BINOL were matched for the high enantioselectivity; the BINOL moiety played a pivotal role in the absolute configuration of the addition products. The nitrogen in pyridine coordinated to the metal center Cu(I) and the 6-Me in pyridine exerted an important effect on the product enantioselectivities. Ligand (S,S)-La afforded good enantioselectivities in the addition reaction of Et2Zn to trans-4-aryl-3-buten-2-one. The ligand (S,S)-Lc was better for chalcones, and up to 97.1 % was achieved. To our knowledge, this was one of the best results in this kind of reactions.We synthesized a new type of Hg-binaphthyl-phosphite-pyridine ligands Lk-Lp and systematically studied their application in Cu(I)-catalyzed 1,4-conjugate additions of EtaZn to enones. The results showed the ligand (S, S)-Ll derived from (S)-H8-NOBIN and (5)-BINOL backbone afforded high enantioselectivities for various chalcones. The corresponding ligand (S,S)-Lk achieved very high ee values for tans-4-aryl-3-buten-2-one substrates, and up to 97.8 % ee has been obtained.To the best of our knowledge, this is the best result for the enantioselective 1,4-conjugate addition of Et2Zn to /raw5-4-aryl-3-buten-2-one.A clear positive nonlinear effect of the enantioselectivity of ligand LA on the product ee was observed in the enantioselective 1,4-conjugate addition. The experimental data met Kagan’s MLj model.We observed a variation of the product absolute configuration with temperature in the Cu(I)-phosphite-pyridine complex catalyzed 1,4-conjugate addition of EtaZn to enones.更多还原