| Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts |
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| 引用本文： | 荆庆 SANDOVAL Christian A. 山口芳树 加藤晃一 丁奎岭.Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts[J].中国化学,2007,25(8):1163-1170. |
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| 作者姓名： | 荆庆 SANDOVAL Christian A. 山口芳树 加藤晃一 丁奎岭 |
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| 作者单位： | [1]State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China [2]Graduate School of Pharmaceutical Sciences, Nagoya City University, Mizuho, Nagoya 467-8603, Japan |
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| 基金项目： | Project supported by the National Natural Science Foundation of China, Chinese Academy of Sciences, the Major Basic Research Development Program of China （No. 2006CB806106）, the Science and Technology Commission of Shanghai Municipality and Merck Research Laboratories. |
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| 摘 要： | We herein report on solution structural studies of Ru^Ⅱ catalysts （3a, 9） composed of achiral bisphosphine ligands （4, 8） and the enantiopure 1,2-diphenylethylenediamine （DPEN）. Complete chiral induction from enantiopure （R,R）-DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non-fluxional （even at 70 ℃） configuration. The coordination of the C=O moiety in 4 to the cationic Run center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity （91% enantiomeric excess） and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2-diamine. Consistent with the hydrogenation product, the （R,R）-DPEN induces a M-conformation （fight-handed） chirality for flexible phosphine ligand 4 in the complex, resulting in a 2,2-configuration about the Ru^Ⅱ center.
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| 关 键 词： | 不对称催化 手性感应 NMR 酮 双磷化氢 钌催化剂 |
| 修稿时间： | 2007-04-132007-05-08 |
Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts |
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| JING Qing,SANDOVAL Christian A,YAMAGUCHI Yoshiki,KATO Koichib,DING Kui-Ling.Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts[J].Chinese Journal of Chemistry,2007,25(8):1163-1170. |
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| Authors: | JING Qing SANDOVAL Christian A YAMAGUCHI Yoshiki KATO Koichib DING Kui-Ling |
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| Institution: | 1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China ;2. Graduate School of Pharmaceutical Sciences, Nagoya City University, Mizuho, Nagoya 467-8603, Japan |
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| Abstract: | We herein report on solution structural studies of RuII catalysts ( 3a , 9 ) composed of achiral bisphosphine ligands ( 4 , 8 ) and the enantiopure 1,2‐diphenylethylenediamine (DPEN). Complete chiral induction from enantiopure (R,R)‐DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non‐fluxional (even at 70 °C) configuration. The coordination of the C?O moiety in 4 to the cationic RuII center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity (91% enantiomeric excess) and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2‐diamine. Consistent with the hydrogenation product, the (R,R)‐DPEN induces a M‐conformation (right‐handed) chirality for flexible phosphine ligand 4 in the complex, resulting in a λ,λ‐configuration about the RuII center. |
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| Keywords: | asymmetric catalysis chiral induction NMR hydrogenation ketone bisphosphine ruthenium |
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