一种高选择性联吡啶双膦配体在烯烃氢甲酰化中的应用研究

A highly regioselective bisphosphine ligand for olefin hydroformylation

本研究以联吡啶为骨架合成了一种双齿膦配体BiPyPhos,通过核磁共振波谱、高分辨质谱和红外分析证实了双膦配体的结构。该配体的设计充分考虑了联吡啶骨架中N原子对骨架电子效应的调节作用,以及对铑配合物结构的调控能力。进一步的催化性能测试表明,该配体与铑原位形成的均相催化剂在催化端烯烃和内烯烃等底物时表现出优异的催化活性、化学选择性和区域选择性。例如,在1-辛烯氢甲酰化反应中,底物转化率高达100.0%,成醛选择性达到88.6%,其正异比高达43。该配体具有柔变的骨架和大的自然咬角,有利于形成空间位阻较小的直链烷基-铑活性物种,从而实现对区域选择性的调控。配体BiPyPhos的成功应用为羰基化反应催化剂的设计与合成提供了新的思路。

A bidentate phosphine ligand,BiPyPhos,based on the pyridine skeleton was synthesized.The structure of the bisphos-phine ligand was confirmed through nuclear magnetic resonance spectroscopy(NMR),high-resolution mass spectrometry(HRMS)and infrared spectroscopy(IR)analysis.The design of this ligand fully considered the modulation effect of the nitrogen atom in the pyridine skeleton on the electronic properties of the ligand and its control ability over the coordination structure formed with rhodi-um.Further hydroformylation performance tests demonstrated that the homogeneous catalyst formed by this ligand and rhodium ex-hibited excellent catalytic activity,chemoselectivity and regioselectivity in the hydroformylation of terminal olefins and internal ole-fins.For example,in the hydroformylation reaction of 1-octene,a conversion rate of 100%was achieved,with an aldehyde yield of 88.6%,and a linear-to-branched ratio was up to 43.The ligand featured a flexible backbone and a large natural bite angle,which facilitated the formation of linear alkyl-rhodium active species with low steric hindrance,thereby achieving good regioselectivity.The successful application of BiPyPhos provided new insights into the design and synthesis of catalysts for carbonylation reactions.