新型C3-含硅基取代手性脯氨酸型催化剂的高效构筑

Efficient Construction of Novel C3-Silyl Substituted Chiral Proline Catalysts

为将C-H活化策略应用于手性有机催化剂的开发,选择以L-脯氨酸为原料、C(sp^(3))-H硅烷化反应为关键步骤,设计合成了两种新型的C3-三甲基硅基取代的手性脯氨酸催化剂,并将其分别应用于对硝基苯甲醛与丙酮的分子间不对称aldol反应和亚胺与β-甲基丁醛的分子间不对称Mannich反应,均可以良好对映选择性实现目标产物的合成.该策略有效丰富了脯氨酸结构的修饰手段,为新型含硅小分子催化剂的开发提供了新方法.

In order to apply the C-H activation strategy to the development of chiral organic catalysts,two novel C3-trimethylsilyl substituted chiral proline catalysts are designed and synthesized using L-proline as the starting material and C(sp^(3))-H silylation as the key step,which are applied to the asymmetric aldol reaction of p-nitrobenzaldehyde with acetone and the asymmetric Mannich reaction of imine withβ-methylbutyraldehyde,respectively.Both target products can be synthesized with a good enantioselectivity.This strategy effectively enriches the means of structural modification of proline and provids a new method for the development of new silicon-containing organic catalysts.