Development of Enantioselective Reactions therough Double Catalytic Activation

为了开发通过使用手性刘易斯酸和胺催化剂的亲电体和亲核体前体的双重催化活化方法，并且进一步为了将新方法应用于对映选择性迈克尔加成反应，已经检查了以下项：1.手性刘易斯酸催化剂综述2.胺类催化剂的正确选择3.给体和受体的正确选择以抑制背景反应4.反应介质的极性对催化效率的影响5.影响催化效率的因素的表征研究发现，由阳离子镍（Ⅱ）衍生的DBFOX/Ph配合物对强配位亲核试剂有很高的耐受性，与大体积胺催化剂联用时，DBFOX/Ph配合物能有效地催化亲电试剂和亲核试剂的反应，从而开辟了一种新的亲电试剂和亲核试剂催化活化方法。因此，一个新的入口，高效的对映选择性迈克尔加成反应，使用硝基甲烷，丙二腈，和环状1，3-二羰基化合物。

In order to develope the double catalytic activation method of both electrophile and nucleophile precursors by using chiral Lewis acid and amine catalysts, and further in order to apply the new method to enantioselective Michael addition reactions, the following terms have been examined :1.survey of torelant and active chiral Lewis acid catalysts2.right selection of amine catalysts3.right selection of donors and acceptors to prohibit the background reactions4.effect of the polarity of reaction media on the catalytic efficiency5.characterization of factors which enhance enantioselectivity and optimization of reaction conditionsIt is found that the DBFOX/Ph complexes derived from cationic nickel(II)s, which show high torelance toward strongly coordinating nucleophiles, work effectively in combination with bulky amine catalysts, so that a new catalytic activation method of both electrophiles and nucleophiles can be developed. Thus, a new entry to highly efficient enantioselective Michael addition reactions using nitromethane, malononitrile, and cyclic 1,3-dicarbonyl compounds.