Mechanistic Studies on Chiral Zinc Complex-Catalyzed Asymmetric Alkylation

手性锌配合物催化不对称烷基化反应机理研究

• 批准号: 05554016
• 负责人: NOYORI Ryoji
• 金额: $ 11.52万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05554016/
• 关键词: Asymmetric Catalysis; Organozinc complexes; Alkylation; Chirality Multiplication; Chirality Amplification; Self Recognition; Nonself Recognition; Mechanism; 炭素-炭素結合形成; 化学的不斉増殖; DAIB

In the presence of a catalytic amount of (-) -3-exo- (dimethylamino) isoborneol (DAIB), reaction of dialkylzincs and aldehydes is accelerated markedly to give, after hydrolysis, the corresponding S alcohols in high enantiomeric purity. In this enantioselective alkylation, nonlinear relationship between optical purities of the chiral source and products. For example, reaction of benzaldehyde and diethylzinc in the presence of 8 mol% of (-)-DAIB in 15% ee leads to (S)-1-phenyl-1-propanol in 95% ee. The mechanisms of chirality multiplication as well as amplification have been elucidated on the basis of the kinetic measurement, alkyl scrambling experiments, single crystal X-ray analysis, 1H-NMR study, molecular-weight determination of certain key intermediates, systematic investigation using DAIB and its stereoisomers. This unusual phenomenon has been understood as a result of a marked difference in chemical properties of the diastereomeric dinuclear complexes formed from dialkylzincs and the DAIB auxiliary, proposing importance of the self and nonself recognition of the asymmetric catalysts. This view is supported the ab initio molecular orbital calculations of the model systems.

在催化量的（-）-3-外-（二甲氨基）异冰片（DAIB）存在下，二烷基锌与醛的反应明显加速，水解后得到相应的高对映体纯度的S醇。在这种对映选择性烷基化反应中，手性源和产物的光学纯度之间存在非线性关系。以苯甲醛和二乙基锌为例，在8mol%（-）-DAIB（ee = 15%）存在下，反应生成（S）-1-苯基-1-丙醇（ee = 95%）。某些关键中间体的分子量测定，使用DAIB及其立体异构体的系统研究。这种不寻常的现象已被理解为由二烷基锌和DAIB助剂形成的非对映体双核配合物的化学性质的显着差异的结果，提出了不对称催化剂的自识别和非自识别的重要性。模型体系的从头计算结果支持了这一观点。

项目成果

P.G.Jessop: "Methyl Formate Synthesis by Hydrogenation of Supercritical Carbon Dioxide in the Presence of Methanol" J.Chem.Soc.,Chem.Commun.707-708 (1995)

P.G.Jessop：“在甲醇存在下通过超临界二氧化碳氢化合成甲酸甲酯”J.Chem.Soc.，Chem.Commun.707-708 (1995)

R.Noyori: "Practical Synthesis of Chiral Secondary Alcohols for the Preparation of Ferroelectric Liquid Crystals" Elsevier. 389-392 (1993)

R.Noyori：“用于制备铁电液晶的手性仲醇的实用合成”Elsevier。

Self and Nonself Recognition of Asymmetric Catalysts. Nonlinear Effects in the Amino Alcohol-Promoted Enantioselective Addition of Dialkylzincs to Aldehydes: "M.Kitamura, S.Suga, M.Niwa, and R.Noyori" J.Am.Chem.Soc.117. 4832-4842 (1995)

不对称催化剂的自我和非自我识别。

Enantiomer Recognition of Asymmetric Catalysts. Thermodynamic Properties of Homochiral and Hererochiral Dimers of the Methylzinc Alkoxide Formed from Dimethylzinc and Enantiomeric 3-exo-(Dimethylamino) isoborneol: "M.Kitamura, S.Suga, M.Niwa, R.Noyori, Z.

不对称催化剂的对映体识别。

R.Noyori: "Enantioselective Addition of Organometallic Reagents to Carbonyl Compounds:Chirality Transfer,Multiplication,and Amplification." Angew.Chem.,Int.Ed.Engl.30. 49-69 (1991)

R.Noyori：“有机金属试剂与羰基化合物的对映选择性加成：手性转移、倍增和放大。”