Development of Highly Selective Asymmetric Reaction Systems Utilizing Transition Metal Complexes

利用过渡金属配合物开发高选择性不对称反应体系

• 批准号: 61470089
• 负责人: YAMAGISHI Takamichi
• 金额: $ 3.65万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470089/
• 关键词: Asymmetric hydrogenation; Dehydrodipeptides; Electrostatic interaction; 1,4- Asymmetric induction; Pd-catalyst; Asymmetric allylation; Enantiotopos-selction; Co-imino acidato complex; 不斉求核付加; 環状アリル化合物の不斉アルキル化

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

1. 脱氢寡肽的不对称氢化：针对Y-phe-(S或R)-AA-OH的不对称氢化，开发了具有氨基部分的新型非手性二膦DPP-AE，Rh - DPP-AE催化剂提供了高立体选择性(84 96%d.e.)，无论DPP-AE和底物之间的静电相互作用的氨基保护基团(Ac或Z)如何，通过详细研究，预计。结论是配体和底物之间的静电相互作用使得复合物能够进行多点识别，从而引起高效的1,4-不对称诱导，选择性强烈依赖于溶剂极性，并且在所检测的醇中甲醇提供了最好的结果。在这些Rh-DPP-AE 系统中观察到对DPP-AE 的-供体基团（o-me 和p-Me）增强了底物特异性。烯丙基化合物：Pd-手性二亚膦酸酯（POP）系统被证明对于环状烯丙基化合物的对映选择性烷基化比对 POP 系统进行修饰以改变配体的电子和空间因子更有效。 POP苯基取代基的间位引入甲氧基或两者不对称膦氧基可有效提高对映选择性。该反应还取决于烯醇阴离子的结构，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了 50% e.e. 3. 亚胺化合物的不对称亲核加成：转化率。考察了Co(III)-氨基酸络合物与xhiral Co(III)-亚氨基酸络合物的合成条件，确定了与氨基酸配合物的结构相对应的脱氢和β-消除。确定了该配合物采用平面亚氨基酸螯合物的<LAMBDA>_2构型。 NaBH4 形成的亚氨基酸络合物以高产率添加光学活性氨基酸络合物。

项目成果

山口素夫: Bull.Chem.Soc.Jpn.60. (1987)

山口元夫：Bull.Chem.Soc.Jpn.60 (1987)。

山岸敬道: "文部省科学研究費補助金一般(B)研究成果報告書「金属錯体を用いた高選択的不斉反応系の開発」" 64 (1988)

Takamichi Yamagishi：“教育部科学研究补助金一般（B）研究结果报告“使用金属配合物开发高选择性不对称反应系统”64（1988）

T. Yamagishi, F. Kaneko, M. Yatagai, and M. Hida: "Asymmetric Allylation to Prochiral Enolate by Pd-Chiral Diphos- phinite Catalyst" Bull. Chem. Soc. Jpn.

T. Yamagishi、F. Kaneko、M. Yatagai 和 M. Hida：“Pd-手性二亚膦酸酯催化剂对前手性烯醇化物的不对称烯丙基化”公报。

M. Yamaguchi;T. Yamagishi;M. Hida: Bull. Chem. Soc. Jpn.60. 1942-1945 (1987)

M.山口；T.

山岸敬道: Bull.Chem.Soc.Jpn.

山岸高道：Bull.Chem.Soc.Jpn。