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

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。

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.