权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Study of the correlation between the structure of auxiliary ligands for transition metal complexes as catalysts and the selectivity in homogeneous catalytic reactions

过渡金属配合物催化剂辅助配体结构与均相催化反应选择性相关性研究

基本信息

批准号：
04403018
负责人：
YAMAMOTO Keiji
金额：
$ 22.66万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1994
项目状态：
已结题

项目摘要

According to the proposed project, the Rh(I)-catalyzed hydroformylation, Pd(0)-catalyzed allylation reaction, and conjugate addition of various organozincates were carried out. Especially, the ligand effects on the chemo-, regio-, as well as stereoselectivity in these reactions were elucidated in terms of both steric and electronic origin. Thus, the report consists of the following items ;1. Novel auxiliary ligands for rhodium(I) complexes and their selectivity in hydroformylation of alkenes-With use of the chiral, chelating phsophorus ligands (L-L) having a wide bite angle (-120ﾟ), [RhH(CO)_2L-L] exhibited high catalytic activity in the hydroformylation of vinylarenes, but with low enantioselectivity.2. Regio- and stereoselectivity in palladium(0)-catalyzed allylation-Pd(0)-catalyzed allylation of 2,7-octadienyl acetate gave rise to a novel five-membered ring formation which crucially relied on acetic acid as a solvent. The novel cyclization via pi-allylpalladium intermediates with stereospecific 1,3-chirality transmission was realized in certain prostaglandin synthesis.3. Conjugate addition of functionalized organozincates and their applications to organic syntheses-Diastereoselective addition of particular(Z)-vinylzincates to 4-alkoxy-2-cyclopentenone, followed by an enolate trapping with propargylic iodide, completed the prostaglandin synthesis.

在此基础上，进行了Rh（I）催化的氢化反应、Pd（0）催化的烯丙基化反应以及各种有机锌酸酯的共轭加成反应。特别是，在这些反应中的化学，区域，以及立体选择性的配体效应阐明在空间和电子起源。因此，本报告由以下项目组成：1.铑（I）配合物的新型辅助配体及其在烯烃加氢催化反应中的选择性--使用具有宽咬合角（-120 °）的手性螯合磷配体（L-L），[RhH（CO）_2L-L]在乙烯基芳烃的加氢催化反应中表现出高的催化活性，但对映选择性较低.钯（0）催化的烯丙基化反应中的区域和立体选择性-Pd（0）催化的2，7-辛二烯乙酸酯的烯丙基化反应产生了一种新的五元环的形成，其关键依赖于乙酸作为溶剂。在前列腺素的合成中，实现了通过π-烯丙基钯中间体进行的具有立体定向1，3-手性传递的新型环化反应.功能化有机锌酸酯的共轭加成及其在有机合成中的应用--特殊的（Z）-乙烯基锌酸酯与4-烷氧基-2-环戊烯酮的非对映选择性加成，然后用炔丙基碘捕获烯醇化物，完成了前列腺素的合成。