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. 脱氢寡肽的不对称加氢：对于Y- phe-(S或R)- aa - oh的不对称加氢，开发了具有氨基部分的新型非手性二膦DPP-AE， Rh - DPP-AE催化剂具有很高的立体选择性（84 96%d.e），而不考虑DPP-AE与底物之间的静电相互作用的氨基保护基（Ac或Z）。通过详细的研究得出结论，配体与底物之间的静电相互作用使配合物能够进行多点识别，从而产生高效的1,4-不对称感应。选择性强烈地依赖于溶剂极性，甲醇提供了最好的结果在所研究的醇。DPP-AE中引入给电子基团（o-me和p-Me）增强了底物特异性。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 -手性二亚膦酸盐（POP）体系对环烯丙基化合物的对映异构选择性烷基化比二膦体系更有效。为了改变配体的电子和空间因子，对POP进行了修饰。在POP的苯基取代基m位上引入甲氧基或两个膦氧基不对称均可有效提高对映选择性。该反应还取决于烯醇阴离子和50%e的结构。用乙基氨基丙二酸二甲基阴离子在甲醇中反应得到。3. 对亚胺类化合物的不对称亲核加成：考察了Co(III)-氨基酸配合物向手性Co(III)-亚胺酸配合物的转化，并根据氨基酸配合物的结构建立了脱氢和< β >-消除的条件。测定了其co -亚胺酸配合物的晶体结构。配合物采用< λ >_2构型，具有一个平面亚胺酸螯合物。用NaBH4还原亚氨基酸合物，获得了一个高收率的光学活性氨基酸酸合物。少

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。