芳环为中继站的接力偶联反应及其双官能团化研究

Relay coupling reactions allow for the formation of more than one chemical bond in a single reaction and thus have high step-economy. Numerous unsaturated functional groups, such as carbenes, mono-olefins, conjugated dienes, and alkynes, have been used as relay stations for relay coupling reactions. However, aromatic rings, which are highly unsaturated, have not yet been used for this purpose. The aim of this project is to study these coupling reactions using furans, which can be obtained from sustainable sources, and other heteroaromatic rings as relay stations. We plan to activate the aromatic rings via rational matching the coupling groups, optimization of the reaction conditions, and fine tuning the electron density of the aromatic rings, so that they have chemical properties similar to those of non-aromatic olefins and will thus be suitable relay stations for the coupling reactions.. The following topics will be investigated as part of this project: product diversity resulting from difunctionalization of the furan diene moiety on the basis of the coupling reaction type and the substrates; control of the stereochemistry of the products of difunctionalization of the furan diene moiety; and product diversity resulting from the use of various aromatic rings as relay stations. We expect this project to pave the way for the development of new dearomatizing transformations of the furan ring and other aromatic rings, new modes for aromatizing reactions, and highly efficient, stereoselective methods for the synthesis of dispiro-lactones, aza-sugars, and amines with a chiral quaternary carbon center.

接力偶联反应（偶联基团通过不饱和基团发生间接偶联）过程涉及多跟化学键的生成，具有高步骤经济性。文献中作为接力偶联反应的中继站主要有卡宾、单烯烃、共轭双烯、炔烃等不饱和基团，但未涉及不饱和度高的芳环作为中继站。本课题拟开展基于呋喃及其他杂芳环作为中继站的接力偶联反应研究。拟通过底物（包括芳环，偶联基团）的合理匹配，条件筛选，芳环电荷密度调控来激活芳环双键，使其具有趋向于普通烯烃的化学性质，可作为一些偶联反应中继站。研究内容包括：基于偶联反应类型和反应底物的多样性实现呋喃双烯双官能团化产物结构多样性；呋喃双烯双官能团化产物立体选择性控制；中继站芳环的多样性实现芳环双键双官能团化产物结构多样性等。本课题将为呋喃及其它杂芳环去芳构化转化开辟新途径，发展一些去芳构化反应的新模式，同时为双螺环内酯、氮杂糖以及含手性季碳的胺类等功能分子提供高效、高立体选择性合成方法。

接力偶联反应（偶联基团通过不饱和基团发生间接偶联）过程涉及多跟化学键的生成，具有高步骤经济性。文献中作为接力偶联反应的中继站主要有卡宾、单烯烃、共轭双烯、炔烃等不饱和基团，但未涉及不饱和度高的芳环作为中继站。本课题开展基于呋喃、吲哚及其他杂芳环作为中继站的接力偶联反应研究。通过对底物（包括芳环，偶联基团）的合理匹配，条件筛选，芳环电荷密度调控来激活芳环双键，使其具有趋向于普通烯烃的化学性质，作为一些偶联反应中继站。研究内容包括：基于偶联反应类型和反应底物的多样性实现呋喃双烯双官能团化产物结构多样性；呋喃双烯双官能团化产物立体选择性控制；中继站芳环的多样性实现芳环双键双官能团化产物结构多样性等。本课题为呋喃及其它杂芳环去芳构化转化开辟新途径，发展一些去芳构化反应的新模式，同时为双螺环缩酮、多取代内酰胺、含双手性季碳螺环吲哚啉酮等功能分子提供高效、高立体选择性合成方法。