新型手性七元氮杂环卡宾的设计合成及应用研究

项目名称： 新型手性七元氮杂环卡宾的设计合成及应用研究

项目编号： No.21302151

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 陈洁

作者单位： 西北大学

项目金额： 25万元

中文摘要： 氮杂环卡宾作为有机小分子催化剂催化的极性翻转反应成为近年来研究的热点领域之一。具有联萘骨架结构化合物如BINOL/BINAP在金属不对称催化领域，联萘手性磷酸、螺环季铵盐类相转移催化剂等在有机小分子催化领域都表现出卓越的催化活性。然而基于此优秀骨架结构的手性氮杂环卡宾催化剂在有机催化领域尚无研究报道。本项目结合手性氮杂环卡宾催化剂的发展以及具有优秀催化活性的联萘骨架结构，设计一系列新型手性卡宾前体化合物：七元环脒盐（1,3-二氮杂卓盐）和"噻唑"盐（1，3-硫氮杂卓盐），并发展出高效制备方法。通过改变氮原子以及联萘骨架3和3'位置的取代基来研究电子效应和位阻效应对此类氮杂环卡宾的稳定性以及催化性能的影响，促进催化剂结构改良，最终发展出性能优异的基于联萘骨架结构的新型手性氮杂环卡宾类催化剂。进而发展出新型不对称安息香缩合，分子内/分子间Stetter反应等催化体系。

中文关键词： 有机催化；合成；不对称催化；氮杂环卡宾；

英文摘要： Umpolung reactions catalyzed by N-Heterocyclic carbenes (NHCs) have become a quickly growing field in the past decade.Compounds bearing binaphthyl skeleton such as BINOL/BINAP have been widely used as excellent ligands in asymmetric organometallic catalysis,both chiral cyclic phosphoric acid diester and spiro ammonium salts derived from BINOL also play important roles as chiral Bronsted acid and phase-transfer catalysts in organocatalysis. However, there is no report on the asymmetric catalysis using such NHC bearing binaphthyl structure as an organocatalyst. Consideration of the development of NHCs and the excellent catalytic capability of binaphthyl skeleton, this project will design a series of novel NHC precursors including seven-member amidinium salts (1,3-diazepinium salts) and "thiazolium salts" (1,3-thiazepine salts), and the efficient synthetic routes for the preparation of them will also be developed. The steric and electronic effect to the stability and catalytic capability of these new type NHCs will be probed by using differenct substituents attached to the nitrogen atom and the 3,3'-positions of binaphthyl structure, then the structrue of NHCs will be improved, finally, the optimal novel chiral NHCs bearing binaphtyl skeleton will be developed. Furthermore, new asymmetric systems, such as benzoin r

英文关键词： organocatalysis；synthesis；asymmetric catalysis；N-Heterocyclic carbenes；