【摘要】 建立了一个不使用有机溶剂的端炔C—H键羧化新体系:在Ag(I)/DBU(1,8-二氮杂二环十一碳-7-烯)催化体系中,通过超临界二氧化碳与端基炔的羧化反应,以较高产率得到了相应丙炔酸产物.在反应体系中,超临界二氧化碳既是反应物又是反应溶剂;助剂DBU起到了碱、亲核体和共催化剂的作用,并能够明显加快反应速率.筛选出的催化体系具有良好的催化反应活性和底物适应能力,能够实现液态、固态端基炔与超临界二氧化碳的直接羧化反应,为制备功能化丙炔酸类化合物提供了一个环境友好、简单、经济的合成路线.更多还原

【Abstract】 A organic solvent free, new carboxylation pathway for C—H bond of terminal alkynes with supercritical CO2(Sc CO2) has been developed by using Ag(I)/DBU(1,8-diazabicyclo(5.4.0)undec-7-ene) catalytic system to obtain propiolic acid products with excellent yields in this work. In our reaction system, Sc CO2 not only acts as reactive solvent but also as reactant. DBU plays the roles of co-catalyst, nucleophile and base, and obviously enhances the reaction rate in Sc CO2. The Ag(I)/DBU catalytic system exhibits higher activity and wide substrate scope. Notably, both liquid and solid terminal alkynes can smoothly react with Sc CO2 to produce desired product. The reaction pathway of functionalized propiolic acid formation from the carboxylation of terminal alkynes with CO2 is environment-friendly, simple, and economic.更多还原