基于1,3-丁二烯双官能团化的不对称多组分和串联反应研究

发展兼具原子、步骤和过程经济性以及高立体选择性和产物结构多样性等理想合成特征的新型不对称多组分和串联反应是当今有机合成化学发展的方向。1,3-丁二烯及其衍生物是来源丰富的大宗有机化工原料，发展1,3-丁二烯参与的新型不对称多组分和串联反应具有重要的理论意义和应用价值。本项目针对1,3-丁二烯衍生物双官能团化反应中存在的问题，利用手性亚膦酰胺配体的钯络合物催化以及钯/手性布朗斯特酸的协同催化，通过1,3-丁二烯衍生物的双官能团化反应，发展一系列新型不对称多组分和串联反应，主要包括：（1）不对称多组分偶联反应；（2）酮和亚胺的不对称烯丙基化反应；（3）不对称串联环化反应；（4）2,4-二烯戊醇衍生物的不对称偶联/重排串联反应。这些反应将为结构多样性地构建多官能团手性分子提供高效方法，并将用于手性多氯代醇中间体和天然产物Mytilipin A及相关结构类似物的不对称合成。

The creation of unprecedented asymmetric multicomponent and cascade reactions featured by the combination of atom-, step- and pot-economy, and also by the high structural diversity and excellent stereoselectivity has been a research topic of current interest in organic synthesis. 1,3-Butadiene and its derivatives are readily available feedstock, and hence the development of new asymmetric multicomponent and cascade reactions of 1,3-butadiene derivatives holds great importance in organic synthesis. This proposal will be focused on the creation of new enantioselective multicomponent transformations by asymmetric difunctionalization of 1,3-butadienes catalyzed by chiral palladium complexes and the palladium/chiral Bronsted acid binary catalyst systems, including (1) multicomponent coupling reaction, (2) asymmetric allylation of ketones and imines, (3) cascade cylization reaction, (4) asymmetric cascade coupling/ rearrangement of 2,4-pentadienol derivatives. The application of the new methods to stereoselective synthesis of chiral polychloro alcohols and a natural product Mytilipin A, together with its structural analogues will also be investigated.