Development of Enantioselective Reactions therough Double Catalytic Activation

为了发展亲电和亲核前体的手性路易斯酸和胺催化剂的双催化活化方法，并进一步将该方法应用于不对称Michael加成反应，考察了以下几个方面的问题：1.手性和活性手性Lewis酸催化剂的概况；2.胺催化剂的正确选择；3.正确选择供体和受体以抑制背景反应；4.反应介质的极性对催化效率的影响5.提高对映体选择性的因素表征和反应条件的优化与体积大的胺催化剂有效结合，从而开发出一种新的亲电性和亲核性的催化活化方法。从而为使用硝基甲烷、丙二腈和环状1，3-二羰基化合物进行高效的不对称Michael加成反应开辟了新的途径。

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.