Kamijo Shin, Jin Tienan, Huo Zhibao, Gyoung Young Soo, Shim Jae-Goo, Yamamoto Yoshinori
Research Center for Sustainable Materials Engineering, Institute of Multidisciplinary Research for Advanced Materials, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Mol Divers. 2003;6(3-4):181-92. doi: 10.1023/b:modi.0000006755.04495.d3.
The synthesis of tetrazoles was achieved via the palladium-catalyzed three component coupling (TCC) reaction; The TCC reaction of malononitrile derivatives, allyl acetate and trimethylsilyl azide proceeds very smoothly under a catalytic amount of Pd(PPh3)4 to give 2-allyltetrazoles, and further the TCC reaction of various activated cyano compounds, allyl methyl carbonate and trimethylsilyl azide proceeds readily under a catalytic amount of Pd2(dba)3 x CHCl3 and (2-furyl)3P to give 2-allyltetrazoles. pi-Allylpalladium azide complex is proposed as a key intermediate in the catalytic cycle and the [3 + 2] cycloaddition between the pi-allylpalladium azide complex and cyano compounds most probably gives the tetrazole frameworks. The deallylation of the derived allyltetrazoles was attained via the two-step procedure; the ruthenium-catalyzed isomerization and ozonolysis.
四唑的合成是通过钯催化的三组分偶联（TCC）反应实现的；丙二腈衍生物、乙酸烯丙酯和三甲基硅基叠氮化物的TCC反应在催化量的Pd(PPh3)4作用下非常顺利地进行，生成2-烯丙基四唑，此外，各种活性氰基化合物、烯丙基碳酸甲酯和三甲基硅基叠氮化物的TCC反应在催化量的Pd2(dba)3·CHCl3和(2-呋喃基)3P作用下很容易进行，生成2-烯丙基四唑。提出π-烯丙基钯叠氮配合物是催化循环中的关键中间体，π-烯丙基钯叠氮配合物与氰基化合物之间的[3 + 2]环加成很可能生成四唑骨架。衍生的烯丙基四唑的脱烯丙基化是通过两步法实现的；钌催化异构化和臭氧分解。
