Development of Multi-Functional Metal-Complex Catalysts for Liquid/Liquid Biphasic Reactions and Their Application to Hydroformylation

双相催化是一种行之有效的催化剂分离和回收方法。以三苯基膦磺酸盐（TPPTS）为配体的水溶性铑络合物催化丙烯氢甲酰化的Ruhrchemie/Rhone-Poulenc工艺在文献中被反复讨论，因为它允许只使用水作为反应介质。然而，它的应用仅限于具有明显水溶性的烯烃。此外，在这个过程中，线性醛是最理想的产物，关键问题是区域选择性的控制。在本课题中，我们的研究重点是设计和制备具有反相转移功能和高区域选择性的金属配合物催化剂的新型水溶性二膦配体。首先，我们设计了4,5-二膦-9,9-二甲基杂蒽的磺化衍生物，每个衍生物上含有一个对（对烷基氧基苯基）苯基烷基。另外两个磷原子，如4,5-二{[对-（对甲氧基苯基）-苯乙基]-苯基磷酸}-9,9-二甲基杂蒽和4,5-二{叔丁基[对-（对甲氧基苯基）苯乙基]-磷酸}-9,9-二甲基杂蒽。磺化衍生物预计不会在水中形成聚集体，而其前体的合成通常是困难的，因为两个磷原子上有三个不同的取代基的p -致氮双膦。作为中间体之一，我们以(rac)-二膦和(meso)-一的混合物制备了4,5-二（硼酸叔丁基膦）-9,9-二甲基杂蒽，并将其分离成两个非对映体。但由于BuLi处理不能产生锂衍生物，因此不适合作为中间体。此外，用胺或酸（如四氟硼酸）处理难以去除硼氧化基团。然后，以二氯苯膦为起始原料，与（对甲氧基苯基）苯乙基氯化镁进行一锅反应，选择性地生成4,5-二（氯苯膦）-9,9-二甲基杂蒽作为中间体，得到目标化合物的前驱体。最后，前体4,5-二{[对-（对甲氧基苯基）苯乙基]-苯基膦}-9,9-二甲基杂蒽作为(rac)-二膦和（中位）-一的混合物得到，并分离成两个非对映体。在前驱体磺化后，我们将利用与磺化配体的rh配合物在水相体系中进行高烯烃的氢甲酰化，以实现高区域选择性。少

Biphasic catalysis is a well-established method for effective catalyst separation and recycling. The Ruhrchemie/Rhone-Poulenc process for the hydroformylation of propene catalyzed by a water-soluble rhodium complex with triphenylphosphane trisulfonate (TPPTS) as a ligand has been repeatedly discussed in the literature, because it allows the exclusive use of water as the reaction medium. However, its application is limited to olefins which have appreciable water solubility. Furthermore, the key issue in this process, where linear aldehydes are the most desired products, is the control of regioselectivity. In this research project, our attention was focused on the design and preparation of novel water-soluble diphosphine ligands for metal-complex catalysts which function inverse phase-transfer catalysts and induce high regioselectivity.First of all, we have designed sulfonated derivative of 4,5-diphosphino-9,9-dimethylxanthene possessing one p-(p-alkyloxyphenyl) phenylalkyl group on each … More two phosphorus atoms, such as 4,5-bis{[p-(p-methoxyphenyl)-phenylethyl]-phenylphosphino}-9,9-dimethylxanthene and 4,5-bis{tert-butyl[p-(p-methoxyphenyl)phenylethyl]-phosphino}-9,9-dimethylxanthene. The sulfonated derivatives would be expected not to form aggregates in water, while syntheses of *eir precursors are generally difficult owing to P-chirogenic bisphosphines with tree different substituent groups on the two phosphorus atoms.As one of intermediates, we have prepared 4,5-bis(boranato-terf-butylphosphino)-9,9-dimethylxanthene as a mixture of (rac)-diphosphine and (meso)-one, and separated it to two diastereomers. However, it was unsuitable as a intermediate, because the treatment with BuLi afforded no lithio derivative. Also, removal of the boranato group was difficult by treatment with amines or acids such as tetrafluoroboric acid. Then, to obtained precursors of the target compounds, one-pot reaction starting from dichlorophenylphosphine was conducted with (p-methoxyphenyl)phenylethylmagnesium chloride, where 4,5-bis(chlorophenylphosphino)-9,9-dimethylxanthene would be formed selectively as an intermediate. Finally, the precursor, 4,5-bis{[p-(p-methoxyphenyl)phenylethyl]-phenylphosphino}-9,9-dimethylxanthene, was obtained as a mixture of (rac)-diphosphine and (meso)-one, and separated to two diastereomers. After sulfonation of the precursor, we will conduct hydroformylation of higher olefins in aqueous biphasic system using Rh-complexes with the sulfonated ligands to realize high regioselectivity. Less