Development of Dynamic Multi-Functional Chiral Molecular Catalysts for Asymmetric Reduction and C-C Bond Formation

用于不对称还原和C-C键形成的动态多功能手性分子催化剂的开发

• 批准号: 12305057
• 负责人: IKARIYA Takao
• 金额: $ 20.61万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12305057/
• 关键词: molecular catalyst; metal amide complex; acid-base cooperative effect; dynamic function; C-H bond activation; transfer hydrogenation; supercritical fluid; C-C bond formation; 金属ヒドリド錯体; 二酸化炭素挿入反応; 不斉クラスター触媒反応; CH結合活性化; 光学活性ジオール; 炭素炭素結合形成反応

A well-defined chiral transition metal amide complex with a M/NH bifunctional unit, Ru(Tsdpen)η^6-arene) or C_p^*M(Tsdpen), (M = Rh, Ir), has sufficient Bronsted basicity to deprotonate 2-propanol or formic acid and acidic organic compounds, leading to a hydrido amine complex and amine complexes bearing a metal bonded C- nucleophile, respectively. Thanks to a rapid and effective interconversion between the amide complex and the amine complex, the chiral amide complex has proven to effect asymmetric transfer hydrogenation of α-substituted aromatic ketones and asymmetric Michael addition to cyclic eneones in a highly stereoselctive manner. The dynamic M/NH bifunctional effect can be applied to the chiral Ru cluster-based catalyst systems generated in situ from Ru_3(CO)_<12> and chiral diiminodiphosphine tetradentate ligands. This chiral cluster effected asymmetric transfer hydrogenation of aromatic ketones in 2-propanol, leading to optically active alcohols with high ee. The dynamic mult … More i-functional effect of both the amide and the amine complexes is responsible for the excellent catalyst performance in terms of high reactivity, selectivity, and practicability.We have demonstrated that supercritical fluids are promising reaction media for molecular catalysis and the utilization of a particular fluid, scCO_2 caused a remarkable enhancement of reactivities and selectivities of molecular catalysts. In order to gain deeper understanding of the reaction mechanism of the molecular catalysis in this unique media, a supercritical fluid nuclear magnetic resonance (scNMR) spectroscopic method has been developed using a commercially available NMR spectrometer equipped with a high-pressure zirconia cell. We found that trialkylphosphite ligands are highly effective for increasing the solubility of dichloropalladium(II) and dichlororuthenium(II) complexes in scCO_2 and the Ru complex promoted rapid vinyl carbamate formation from phenylacetylene, diethylamine, and scCO_2. The scNMR investigation on a dynamic behavior of diethylamine in scCO_2 revealed that formation of N, N-diethylcarbamic acid was reversible and the concentration of the carbamic acid was highly influenced by the pressure and temperature. Less

A well-defined chiral transition metal amide complex with a M/NH bifunctional unit, Ru(Tsdpen)η^6-arene) or C_p^*M(Tsdpen), (M = Rh, Ir), has sufficient Bronsted basicity to deprotonate 2-propanol or formal acid and acidic organic compounds, leading to a hydrido amine complex and amine complexes bearing a metal bonded C-分别是亲核试剂。感谢您在酰胺复合物与胺复合物之间的快速有效相互转换，手性酰胺复合物已被证明可以在高度立体的观念方式中实现α-取代的芳族酮的不对称转移氢化，并在高度立体的环境中添加了环环烯酮的不对称迈克尔。动态M/NH双功能效应可以应用于由RU_3（CO）_ <12>和手性二氨基二磷脂的原位产生的基于手性RU簇的催化剂系统。这种手性簇影响了2-丙醇中芳族酮的不对称转移氢化，从而导致具有高EE的光学活性醇。酰胺和胺配合物的动态多...在高反应性，选择性和实践方面都使催化剂的表现出色。为了更深入地了解这种独特的介质中分子催化的反应机制，已经使用配备有高压锆细胞的市售NMR光谱仪开发了超临界流体核磁共振（SCNMR）光谱法。我们发现，试验二氯苯二甲酸盐配体在SCCO_2中提高二氯丙基（II）和二氯苯二苯二氯乙烯（II）络合物的溶解度非常有效，RU复合物促进了从苯基乙烯，二甲基胺和SCCO_2中促进了快速的碳酸碳酸盐形成。 SCNMR对SCCO_2中二乙胺的动态行为的研究表明，n，N-二乙基加仑酸的形成是可逆的，氨基甲酸的浓度受压力和温度的高度影响。较少的

项目成果

Y. Kayaki, T. Torii, K. Izawa, R. Noyori, T. Ikariya: "NMR Observation of Trialkylphosphite-Palladium(II) and Ruthenium(II) Complexes in Supercritical Carbon Dioxide"Chem. Lett.. 424-425 (2002)

Y. Kayaki、T. Torii、K. Izawa、R. Noyori、T. Ikariya：“亚磷酸三烷基酯-钯(II) 和钌(II) 配合物在超临界二氧化碳中的NMR 观察”Chem。

K.Murata, Hirokazu Konishi, Masato Ito, Takao Ikariya: "Deprotonation of Organic Compounds Bearing Acid Protons Promoted by Metal Amido Complexes with Chiral Diamine Ligands Leading to New Organometallic Compounds"Organometallics. 21. 253-255 (2002)

K.Murata、Hirokazu Konishi、Masato Ito、Takao Ikariya：“由金属氨基配合物与手性二胺配体促进的带有酸质子的有机化合物的去质子化，导致新的有机金属化合物”有机金属化合物。

碇屋隆雄, 榧木啓人, 佐古猛編著: "超臨界二酸化炭素の利用技術 第3章第1節"超臨界流体-環境浄化とリサイクル・高効率合成の展開-(アグネ承風社). 123-137 (2001)

Takao Ikariya、Hiroto Kaiki、Takeshi Sako（编）：“超临界二氧化碳利用技术第 3 章第 1 部分”超临界流体 - 环境净化、回收和高效合成的发展 - (Agne Seifusha) 123-137 (2001)。

碇屋隆雄, 基礎錯体工学研究会: "新版錯体化学 基礎と最新の展開"講談社サイエンティフィク. 185-190 (2002)

Takao Ikariya，基础配位工程研究小组：“新版配位化学：基础知识和最新发展”讲谈社科学 185-190 (2002)。

Masato Ito, Makoto Hirakawa, K. Murata, Takao Ikariya: "Hydrogenation of Aromatic Ketones Catalyzed by (η^5-C_5(CH_3)_5)Ru Complexes Bearing Primary Amines"Organometallics. 20. 379-381 (2001)

Masato Ito、Makoto Hirakawa、K. Murata、Takao Ikariya：“含伯胺的 (η^5-C_5(CH_3)_5)Ru 配合物催化芳香酮的氢化”有机金属学 20. 379-381 (2001)。