Carbohydrate-substituted triarylphosphanes - A new class of ligands for two-phase catalysis
Carbohydrate-substituted triarylphosphanes - A new class of ligands for two-phase catalysis
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DOI：
10.1002/anie.199707721
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发表时间：
1997-04-18
期刊：
影响因子：
--
通讯作者：
Zapf, A
中科院分区：
文献类型：
--
作者：
Beller, M;Krauter, JGE;Zapf, A
均相催化的两个基本问题--催化剂的分离和循环利用--可以用两相催化很好地解决。这里，催化剂处于有机产物不溶于其中的亲水相中。为了实现这一原则，有必要开发新的配体，可溶于亲水相。由Kuntz制备的二苯基膦基乙酸[2]和TPPTS配体（TPPTS =三苯基膦三磺酸盐的三钠盐）[31]用作这些开发的起点;如今，它们以吨级规模生产用于最重要的工业两相工艺-壳牌高级烯烃工艺（SHOP）[21]和用于丙烯加氢成丁醛的Ruhrchemie/Rhhe-Poulenc工艺。[41丁二烯调聚（Kuraray）c51和烯丙基取代（Rhbne-Poulenc）r61是两相催化技术应用的另外两个实例。目前在实验室规模上用于胺化、羰基化、氢化、甚至生物有机应用的新开发的方法用于说明两相催化剂在均相催化领域中的热门性。为了获得配体在极性介质（特别是水）中的足够溶解度，通常使用离子基团（磺酸和羧酸、季氨基烷基/芳基和鏻盐）作为膦中的取代基。相反，非离子配体，如膦基醇、具有聚醚取代基的膦、冠醚取代的膦[13]和二苯基膦烷基取代的碳水化合物[12]的使用程度较低。在这里，我们提出了一类新的极性，亲水性triarylphosphanes两相催化，这些化合物的亲水性是由于糖部分。我们已经使用了葡萄糖、半乳糖和葡糖胺的芳基-β-O-糖苷。
The two basic problems of homogeneous catalysis-separation and recycling of the catalyst-can be elegantly solved by using two-phase catalysis.['l Here, the catalyst is in a hydrophilic phase in which the organic products are insoluble. In order to implement this principle, it was necessary to develop new ligands that are soluble in hydrophilic phases. Diphenylphosphinoacetic acidc2] and the TPPTS ligand (TPPTS= trisodium salt of triphenylphosphane trisulfonate),[31 which was prepared by Kuntz, served as the starting points for these developments; nowadays they are produced on the tonne-scale for the most important industrial two-phase processes-the Shell Higher OIefin Process (SHOP)[21 and the Ruhrchemie/Rhhe-Poulenc process for the hydroformylation of propene to butyraldehyde.[41 Butadiene telomerization (Kuraray) c5l and ally1 substitution (Rhbne-Poulenc) r61 are two further examples of the technical application of two-phase catalysis. Newly developed methods, which are currently used on the laboratory-scale for aminations,['] carbonylations,[*] hydrogenations,['] and even bioorganic applications [" l serve to illustrate the topicality of two-phase catalysts in the field of homogeneous catalysis. In order to attain sufficient solubility of the ligands in polar media (particularly water), ionic groups (sulfonic and carboxylic acids, quaternary aminoalkyl/aryl groups, and phosphonium salts) are usually used as substituents in the phosphanes. In contrast, nonionic ligands, such as phosphino alcohols,[''I phosphanes with polyether substituents, I'21 crown ether substituted phosphanes,[13] and diphenylphosphinoalkyl-substituted carbohydrates,[l2'I are used to a lesser extent. We present here a new class of polar, hydrophilic triarylphosphanes for two-phase catalysis; the hydrophilic character of these compounds is attributed to a sugar moiety. We have employed aryl-fi-0-glycosides of glucose, galactose, and glucosamine.