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

根据该方案，进行了Rh(I)催化的氢甲酰化反应、Pd(0)催化的烯丙基化反应以及各种有机锌盐的共轭加成反应。特别是从立体起源和电子起源两个方面阐明了配体对这些反应的化学选择性、区域选择性以及立体选择性的影响。因此，本报告包括以下内容：1.新型Rh(I)配合物辅助配体及其在烯烃氢甲酰化反应中的选择性--利用具有较大咬合角(-120ﾟ)的手性螯合膦配体(L-L)，[RHH(CO)_2L-L]在乙烯氢甲酰化反应中表现出较高的催化活性，但对映体选择性较低。钯(0)催化的烯丙化反应中的区域和立体选择性-钯(0)催化的2，7-辛二烯基乙酸酯的烯丙化反应产生了一个新的五元环的形成，该环的关键依赖于醋酸作为溶剂。在某些前列腺素的合成中，通过具有立体特异性的1，3-手性传递的聚烯丙基钯中间体实现了新颖的环化反应。官能化有机锌盐的共轭加成及其在有机合成中的应用--特定的(Z)-乙烯基锌酸盐与4-烷氧基-2-环戊酮的非对映选择性加成，然后用丙叉碘化物进行烯醇捕获，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.