Development of Enantioselective Reactions therough Double Catalytic Activation

为了利用手性路易斯酸和胺催化剂建立亲电试剂和亲核试剂前体的双催化活化方法，并进一步将新方法应用于对映选择性迈克尔加成反应，本文研究了以下术语：1。相关及活性手性路易斯酸催化剂的研究进展[j]。胺类催化剂的正确选择正确选择供体和受体，防止本底反应。反应介质极性对催化效率的影响提高对映体选择性的因素表征及反应条件优化研究发现，阳离子镍（II）s衍生的DBFOX/Ph配合物对亲和性强的亲核试剂具有较高的耐受性，与大体积胺类催化剂联合使用效果显著，从而为亲电试剂和亲核试剂的催化活化开辟了新的途径。因此，使用硝基甲烷，丙二腈和环1,3-二羰基化合物进行高效对映选择性迈克尔加成反应的新入口。

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.