碱脱除氯化氢制备膦烯的合成方法及其反应性的研究

项目名称： 碱脱除氯化氢制备膦烯的合成方法及其反应性的研究

项目编号： No.21502099

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 段莉莉

作者单位： 南开大学

项目金额： 21万元

中文摘要： 膦烯作为碳卡宾的膦类似物，是一类重要的有机膦试剂。然而膦烯合成化学中存在前体化合物制备复杂、合成方法适用范围窄的问题，并进一步限制了膦烯的性质研究。本申请项目拟利用碱脱除氯化氢的策略, 发展一种步骤简单、条件温和、适用范围广的膦烯合成方法。同时通过对膦烯取代基的筛选，分离出稳定的膦烯化合物。通过Lewis酸络合的亲电性膦烯对分子间C–H键的插入活化、与不饱和底物的环加成反应，为新型有机膦化合物的合成提供新途径。通过Lewis碱配位的亲核性膦烯与过渡金属化合物络合反应的研究，合成多种亲核性膦烯配位的过渡金属化合物，为亲核性膦烯配位的过渡金属催化剂性能的研究提供实验和理论基础。

中文关键词： 膦烯；脱氯化氢；环加成；碳–氢键活化；络合反应

英文摘要： Phosphinidene, as the analogue of carbene, is a class of organophosphane compounds of great importance. However the synthetic problems on the phosphinidene inhibit the investigation of phosphinidene properties, which include the complicated preparation of precursors and very limited scope of methods. In this program, a new synthetic route of dehydrochlorination by base is developed to generate phosphinidene, which leads to a simple, mild and wide-used method. Through screening the substituents, the stable phosphinidenes are able to be isolated. The reactivity of electrophilic phosphinidene complexed by Lewis acid will be studied, including the insertion reaction to the intermolecular C–H bond and the cycloaddition reaction with unsaturated substrates. Meanwhile, the phosphinidene-transition metal complexes will be also synthesized via the complexation reaction of nucleophilic phosphinidene coordinated by Lewis base with transition metal complexes, which provide the theoretical and experimental support for the research of transition-metal catalysts coordinated by the nucleophilic phosphinidene.

英文关键词： phosphinidene;dehydrochlorination;cycloaddition;C–H bond activation;complexation reaction