手性伯胺催化的α-取代乙烯基醛/酮化合物的不对称转化反应研究

项目名称： 手性伯胺催化的α-取代乙烯基醛/酮化合物的不对称转化反应研究

项目编号： No.21502198

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 无机化学

项目作者： 付年凯

作者单位： 中国科学院化学研究所

项目金额： 22万元

中文摘要： 手性伯胺催化已成为不对称催化领域的中坚力量。本课题以烯胺中间体的不对称质子化反应为切入点，结合反应动力学及理论计算等机理研究手段，深入探讨手性伯胺催化α-取代的乙烯基醛酮类化合物的不对称转化的动力学特征及手性控制模式。将根据机理研究的结果，有针对性的合成一类新型手性伯胺催化剂。在此基础之上，拟进一步拓展其他亲核试剂与α-取代的乙烯基醛酮类化合物的加成/不对称质子化反应、α-取代的乙烯基醛酮类化合物与自由基的不对称加成反应及该类底物的不对称氢化反应。

中文关键词： 手性伯胺；机理研究；烯胺质子化；α-取代乙烯基酮；α-取代丙烯醛

英文摘要： Recent advances in primary amine catalysis have provided new synthetic opportunities and conceptual perspectives for successfully attacking major challenges in carbonyl compound chemistry, such as the asymmetric transformation of α-substituted unsaturated aldehydes or ketones, which traditional approaches have not been able to address. In this context, we wish to focus on the mechanistic study of asymmetric transformation of α-substituted unsaturated aldehydes or ketones by using primary amines as the catalysts. Based on the mechanistic results, new primary amine catalysts with superior performance and broad applicability with α-substituted unsaturated carbonyls will be developed. After that, these primary amine catalysts will be applied in the following reactions, such as asymmetric conjugate addition/ enamine protonation reactions with new challenging nucleophiles to α-substituted unsaturated carbonyls, asymmetric reduction of α-substituted unsaturated carbonyls and asymmetric radical addition reactions.

英文关键词： primary amine catalysis;mechanistic study;enamine protonation;α-substituted vinyl ketones;α-substituted acroleins