二茂铁烯丙基钯卡宾络合物的合成及其催化性能

Synthesis and catalytic properties of a ferrocenyl allyl carbene palladium complex

采用"一锅法"用1,3-双(2,6-二异丙基苯基)氯化咪唑对二茂铁烯丙基钯二聚体Ⅰ在室温下进行解聚,不仅简便、高效地合成了二茂铁烯丙基钯卡宾络合物Ⅱ,而且避免了使用不稳定的卡宾。通过IR、1HNMR、13CNMR、MS、HRMS和X射线单晶衍射对其结构进行鉴定。络合物Ⅱ对空气和湿气稳定,且对芳基氯代物参与的Suzuki-Miyaura偶联反应和Buchwald-Hartwig胺化反应展现较高的催化活性。在反应温度70℃、0.4%(以氯代芳烃物质的量为基准计算得到,下同)络合物Ⅱ催化芳基氯代物与芳基硼酸的偶联反应时,产物收率为92%~100%;在反应温度100℃、0.5%络合物Ⅱ催化氯苯与多样化胺的偶联反应时,获得38%~99%的收率。

One pot method was used to depolymerize ferrocenyl allyl palladium dimerⅠwith 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride(IPrHCl)at room temperature,which was not only simple and efficient to synthesize a new ferrocene allyl carbene palladium complexⅡ,(N-heterocyclic carbene)Pd(ferrocenyl-allyl)Cl,but also avoided the use of unstable carbene.The complexⅡwas characterized by IR,1 HNMR,13 CNMR,MS,HRMS and X-ray single crystal diffraction.ComplexⅡis stable to air and moisture,and displays high catalytic activities for Suzuki-Miyaura coupling reaction and BuchwaldHartwig amination of aryl chlorides.When the coupling reactions between different aryl chlorides and different aryl boric acid were carried at 70℃using molar fraction 0.4%(based on the dosage of aryl chlorides,the same below)of complexⅡ,the yields of the products were 92%~100%.At 100℃,the coupling reactions of chlorobenzene with various amines in the presence of 0.5%complexⅡgave the products in yields of 38%~99%.