Development of Highly Selective Asymmetric Reaction Systems Utilizing Transition Metal Complexes

1.脱氢寡肽的不对称氢化反应：对于Y- phe-（S或R）-AA-OH的不对称氢化反应，开发了一种新型的具有氨基结构的非手性双膦DPP-AE催化剂，该催化剂具有较高的立体选择性（84 96% d. e.）不考虑氨基保护基（Ac或Z），其中预期DPP-AE和底物之间存在静电相互作用。通过详细的研究，我们得出结论，配体和底物之间的静电相互作用，使一个多点识别的配合物，导致高效的1，4-不对称诱导。的选择性是强烈依赖于溶剂的极性和甲醇提供了最好的结果之间的醇检查。给电子基团（o-Me和p-Me）的引入增强了DPP-AE的底物专一性。在这些Rh-DPP-AE体系中观察到选择性对温度的特定依赖性。2.环烯丙基化合物的不对称烷基化：Pd-手性二次膦酸酯（POP）体系， ...更多信息 与双膦体系相比，E对环烯丙基化合物的对映体选择性烷基化反应更有效。POP进行了修改，以改变电子和空间因子的配体。在POP的苯基间位引入甲氧基或使两个膦氧基不对称化可有效提高对映体的选择性。反应还依赖于烯醇阴离子的结构和50%e. e.在甲醇中使用乙酰氨基丙二酸二甲酯阴离子的反应中获得。3.亚胺化合物的不对称亲核加成反应：考察了Co（Ⅲ）-氨基酸配合物转化为手性Co（Ⅲ）-亚胺酸配合物的反应，并<beta>根据氨基酸配合物的结构确定了脱氢和消除反应的条件。测定了配合物的晶体结构。该配合物为<LAMBDA>平面的亚氨基酸螯合物，呈a_2构型。用NaBH_4还原亚氨基酸络合物，高产率地得到光学活性的氨基酸络合物。少

1. Asymmetric hydrogenation of dehydrooligopeptides: For the asymmetric hydrogenation of Y- phe-(S or R)-AA-OH, novel achiral diphosphine DPP-AE having amino moiety was developed, and Rh - DPP-AE catalyst afforded high stereoselectivities(84 96%d.e.) irrespective of the amino protecting groups(Ac or Z) where electrostatic interaction between DPP-AE and substrate was expected. By detailed studies, it was concluded that the electrostatic interaction between ligand and substrate enabled a multi-points recognition by the complex to cause highly efficient 1,4-asymmetric induction. The selectivity was strongly dependent on the solvent polarity and methanol afforded best results among alcohols examined. Introduction of electron-donating group(o-me and p-Me) to DPP-AE enhanced the substrate-specificity. Specific dependency of the selectivity on the temperature was observed in these Rh-DPP-AE systems. 2. Asymmetric alkylation of cyclic allylic compounds: Pd-chiral diphosphinite(POP) systems wer … More e proved to be more effective for the enantiotopos-selective alkylation of cyclic allylic compounds than diphosphine systems. POP was modified in order to alter the electronic and steric factors of the ligand. Introducton of methoxly group to the m-position of the phenyl substituent of POP or unsymmetrization of the two phosphinoxy groups was effective to raise the enantio-selectivity. The reaction was also dependent on the structure of the enolate anion and 50%e.e. was obtained in the reaction using dimethyl acetylaminomalonate anion in methanol. 3. Asymmetric nucleophilic addition to imine compounds: The conversion of Co(III)- amino acidato complex to xhiral Co(III)-imino acidato complex was examined, and the conditions of dehydrogenation and <beta>-elimination were established corresponding to the structure of the amino acidato complexes. The crystal structure of thr Co-imino acidata complex was determined. The complex adopted a <LAMBDA>_2 configuration with a planar imino acidato chelate. Reduction of the imino acidato complex by NaBH4 addorded an optically active amino acidato complex in a high yield. Less