基于连串反应一步合成黄酮的双功能化离子液体构筑及催化机制研究

Research on the construction of special functional ionic liquids(shot for ILs) catalysts for one-pot cascade catalysis containing two or more distinct catalytic transformations to construct complex and important molecules under eco-benign conditions has significance and becomes a huge challenge in organic chemical engineering. As a kind of very imprtant natural heterocyclic compounds, flavones have great demand in medicine, food and cosmetics industry. The synthetic route using aldehydes as simple raw materials is still at least through two steps reactions to get the final product of flavnoes, the 2’-hydroxychalcones or flavanones thus have to be separately prepared. In this case, and on the basis of preliminary results in our group, research will be carried out through structure design and construction of OABF-ILs, investigation on process parameters of the one-pot synthesis of flavones in the present of OABF-ILs and mechanism exploration. It will be also carried out further investigation on the catalytic performance of OABF-ILs catalysts in the synthesis of similar structure of flavones and other reactions. It is expected to achieve innovative results in the new functional design of OABF-ILs, catalytic mechanism of OABF-ILs catalysts, the influence of structure regulation on catalytic properties and establishment of a green methodology for highly efficient one-pot synthesis of flavones It is believed that this proposal may provide a reference for further development of these specific functional OABF-ILs catalysts in organic catalysis.

构筑功能化离子液体催化两个或多个不同反应实现连串反应一步合成含有复杂杂环的有机分子是近年来有机化工领域的新挑战。黄酮作为一类重要的天然杂环化合物有着巨大的市场需求。以醛类为原料的合成路线目前仍至少需要两步反应才能得到黄酮。在结合前期工作基础上，本项目利用金属氧酸根的氧化性和弱碱性，创新性提出构筑氧化/碱性双功能离子液体催化剂（简称OABF-ILs），以期实现催化连串反应一步高效合成黄酮。围绕该思路，展开OABF-ILs催化剂的结构设计、化学构筑及其物性表征、OABF-ILs催化连串反应一步合成黄酮机制、OABF-ILs催化连串反应一步高效合成黄酮的工艺参数及拓展等研究，最终获得一步高效催化合成黄酮的工艺参数，阐明OABF-ILs的结构与与催化活性之间的构效关系，揭示OABF-ILs催化连串反应一步合成黄酮的催化机制，并进一步拓宽功能化离子液体在有机催化和天然产物绿色合成领域的应用及发展。

构筑功能化离子液体催化两个或多个不同反应实现连串反应一步合成含有复杂杂环的有机分子是近年来有机化工领域的新挑战。本项目利用金属氧酸根的弱碱性以及在氧化过程中特有的催化性能，成功发展了一种新型的具有热激活活化分子氧的离子液体催化剂，实现了高效绿色催化连串反应一步合成黄酮。通过对这类热激活离子液体催化剂的结构设计、化学构筑及其物性表征；总结了离子液体结构对其催化连串反应一步合成黄酮性能的影响规律；研究了催化剂在催化连串反应一步合成黄酮的催化机制；优化了连串反应一步高效合成黄酮的工艺参数；进一步合成出了具有热激活NHC前体的离子液体催化剂，成功应用于苯甲酸脂、苯并杂环等精细有机化工产品的合成反应中。拓宽功能化离子液体在有机催化和天然产物绿色合成领域的应用及发展。