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.

根据拟议的项目，进行了RH（I）催化的氢甲基化，Pd（0）催化的诱链反应，并添加各种有条件的添加。尤其是，根据空间和电子起源，阐明了这些反应中化学，区域的配体影响以及这些反应中的立体选择性。这是由以下项目组成的； 1。用于硫磺配合物（I）复合物的新型辅助配体及其在烷烃中的选择性，并使用手性，螯合phsophorus cimands（l-l）具有较大咬合角（-120 ﾟ），[RHH（CO）_2L-L]在水中的高催化活性的高催化活性的vInylyr.2钯（0）催化的烯丙基酰基-PD（0）催化的烯丙基化丙烯酸酯的区域和立体选择性引起了一种新颖的五元环形成，这在乙酸作为溶液上非常重要。在某些前列腺素合成中实现了通过立体特异性1,3血压传递的Pi-Alylpalladium中间体的新型环化。3。共轭添加功能化的有条件及其在有机合成 - 二肌选择性上的应用中，将特定（Z） - 乙烯基元素添加到4-Alkoxy-2-cyclopentenone中，然后用丙泊抗碘化物的弹性诱捕，完成了Prostaglandin合成。