蒙脱土负载Pd/Cu双金属纳米微粒催化Sonogashira偶联反应  

Montmorillonite Supported Pd/Cu Bimetallic Nanoparticle Catalyzed Sonogashira Coupling

作　　者：徐伟[1] 孙原龙[1] 郭萌涵[1] 张伟强[1] 高子伟[1] 

机构地区：[1]陕西师范大学化学化工学院,西安710062

出　　处：《有机化学》2013年第4期820-826,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21271124;21041004;20771071);教育部新世纪优秀人才项目支持计划(No.NCET-07-0528);中央高校基本业务费(Nos.GK201004010;GK201002031);"春笋计划"(No.2010-2011西安中学)资助项目~~

摘　　要：为了证实过渡金属催化碳碳键交叉偶联反应的双金属效应,首次研究蒙脱土负载纳米钯铜双金属微粒催化Sonogahira交叉偶联反应.结合蒙脱土重金属吸附特性与DMF溶剂热羰化还原,发展了一种新的双金属纳米微粒合成方法,制备了钯铜比例为1∶1的双金属纳米微粒.催化条件优化实验发现,乙二醇二甲醚/水(V∶V=1∶4)混合体系为最佳溶剂.碳酸钾与三苯基膦存在下,MMT@Pd/Cu高效催化芳基碘与系列端炔的交叉偶联反应,以较好产率分离得到15个炔烃衍生物.动力学研究表明,水对蒙脱土片层的溶胀作用与Pd/Cu双金属协同效应是该催化剂高活性的关键.To demonstrate the bimetallic effect of transition metal catalyzed C-C cross coupling, the montmorillonite （MMT） supported mixed palladium and copper nanoparticles were prepared and applied to catalytic Sonogashira couplings. A new method of preparing mixed metal nanoparticles was invented based on unique metal ion adsorption capacity of mont- morillonite and sequential reductive carbonylation via therrnolysis of N,N-dimethylformide, and POdCu bimetallic nanoparti- cals was prepared in the ratio of 1 ; 1. A mixed solvent system, dimethoxyethane/water （V ： V= l ： 4） was identified as the best solvent of the catalytic coupling. MMT@Pd/Cu catalyzed efficiently the cross-coupling of aryl iodides and terminal aryl- and alkyl-ynes in presence of potassium carbonate and triphenyl phosphine. 15 cross-coupling yne derivatives were isolated in excellent to moderate yields. Experimental kinetic study reveals that both swelling of montmorillonite promoted by water and Pd/Cu bimetallic synergistic effect play critical roles in high activity of the catalyst.

关 键 词：过渡金属催化 蒙脱土 碳-碳键交叉偶联 双金属效应 

分 类 号：O643.32[理学—物理化学]