Heuzé Karine, Méry Denise, Gauss Dominique, Blais Jean-Claude, Astruc Didier
Nanosciences and Catalysis Group, LCOO, UMR CNRS No. 5802 University Bordeaux I, 351 cours de la Libération, 33405 Talence, France.
Chemistry. 2004 Aug 20;10(16):3936-44. doi: 10.1002/chem.200400150.
A series of bis(tert-butylphosphine)- and bis(cyclohexylphosphine)-functionalized Pd(II) monomers and polyamino (DAB) dendritic catalysts were synthesized and investigated for Sonogashira carbon-carbon coupling reactions in a copper-free procedure. The influence of phosphine substituents (tBu versus Cy) on the reaction kinetics was investigated by a GPC technique to monitor the reactions. The dendritic catalysts containing the cyclohexylphosphine ligands could be recovered and reused without loss of efficiency until the fifth cycle. The dendritic Pd(II) catalysts show a negative dendritic effect, that is, the catalyst efficiency decreases as the dendrimer generation increases.
合成了一系列双（叔丁基膦）和双（环己基膦）官能化的钯（II）单体以及聚氨基（DAB）树枝状催化剂，并对其在无铜条件下的Sonogashira碳-碳偶联反应进行了研究。通过凝胶渗透色谱（GPC）技术监测反应，研究了膦取代基（叔丁基对环己基）对反应动力学的影响。含有环己基膦配体的树枝状催化剂可以回收并重复使用，直至第五次循环时效率仍无损失。树枝状钯（II）催化剂表现出负的树枝状效应，即随着树枝状聚合物代数的增加，催化剂效率降低。
