Development and Application of the Highly Efficient and Highly Stereoselective Synthetic Methods for Optically Active Cyelic Compounds by Asymmetric cycloaddition Reactions

光学活性环状化合物的不对称环加成反应高效、高立体选择性合成方法的开发及应用

• 批准号: 08640678
• 负责人: UKAJI Yutaka
• 金额: $ 1.47万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640678/
• 关键词: allylic alcohol; tartaric acid ester; optically active; 2-isoxazoline; nitrile oxide; nitrone; cyclopropane; cycloaddition reaction; 電子吸引基; γ-アミノアルコール; β-ヒドロキシケトン; イソオキサゾリジン

It is strongly required to develop a practical and efficient method for the construction of chiral molecules to explore new biologically active medicines and agricultural chemicals. It is obvious that the design of the specific chiral environment utililzing the chiral auxiliaries whose both enantiomers are easily available provides a useful way to prepare various optically active chemicals. Among such chiral auxiliaries, tartaric acid ester is one of the most promising and readily available candidates.In this research, a new and novel chiral system possessing two metal centers utilizing tartaric acid esters was designed ; that is, if two reactants are bound to two different metal centers of the dialkoxide derived from tartaric acid ester, which might actually form the rigid 5/5-fused bicyclic dinucleating structure, they might be ideally oriented and/or activated by the metals and the following reaction might proceed in an enantioselective manner to afford the corresponding optically active products. According to this hypothesis, we could develop an asymmetric Simmons-Smith reaction, asymmetric 1,3-dipolar cycloaddition reactions of nitrile oxides and nitrones. Easy availability of (R,R)- and (S,S) -tartaric acid esters has now made it possible to prepare both enantiomers of the required chemicals by quite simple procedures.

开发实用、高效的手性分子构建方法是开发新型生物活性药物和农药的迫切需要。显然，利用两种对映体都容易获得的手性助剂设计特定的手性环境，为制备各种光学活性化合物提供了一条有用的途径。在众多的手性助剂中，酒石酸酯是最有前途和最容易获得的手性助剂之一，本研究设计了一种新型的酒石酸酯手性双金属中心体系;也就是说，如果两种反应物与衍生自酒石酸酯的二烷氧基化合物的两个不同的金属中心结合，这实际上可能形成刚性5/5-稠合双环双核结构，它们可以被金属理想地定向和/或活化，并且随后的反应可以以对映选择性的方式进行，得到相应的光学活性产物。根据这一假设，我们可以发展不对称Simmons-Smith反应，腈氧化物和硝酮的不对称1，3-偶极环加成反应。（R，R）-和（S，S）-酒石酸酯的容易获得现在使得可以通过非常简单的方法制备所需化学品的两种对映体。

项目成果

Y.Ukaji, Y.Shimizu, Y.Kenmoku, A.Ahmed, and K.Inomata: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Esters as a Chiral Auxiliary" Chem.Lett.1997. 59-60 (1997)

Y.Ukaji、Y.Shimizu、Y.Kenmoku、A.Ahmed 和 K.Inomata：“利用酒石酸酯作为手性助剂，二烷基锌与硝酮的催化不对称加成反应”Chem.Lett.1997。

Y.Ukaji: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Ester as a Chiral Auxiliary." Chem.Lett.59-60 (1997)

Y.Ukaji：“利用酒石酸酯作为手性助剂，催化二烷基锌与硝酮的不对称加成反应。”

Y.Ukaji, Y.Kenmoku, and K.Inomata,: "Asymmetric Addition Reaction of Organozinc Reagents to Nitrones Using a Catalytic Amount of External Chiral Auxiliary" Tetrahedron : Asymmetry. 7. 53-56 (1996)

Y.Ukaji、Y.Kenmoku 和 K.Inomata，：“使用催化量的外部手性辅助剂进行有机锌试剂与硝酮的不对称加成反应”四面体：不对称性。

Y.Ukaji,M.Miyamoto,M.Mikuni,S.Takeuchi,and K.Inomata: "Asymmetric Bis (alkoxycarbonylation) Reaction of Homoallylic Alcohols Catalyzed by Palladium in the Presence of Cu(I) Triflate Using the Chiral Bioxazoline Ligand" Bull.Chem.Soc.Jpn.69. 735-742 (1996)

Y.Ukaji、M.Miyamoto、M.Mikuni、S.Takeuchi 和 K.Inomata：“使用手性二恶唑啉配体，在三氟甲磺酸铜 (I) 存在下，钯催化高烯丙醇的不对称双（烷氧基羰基化）反应”公报

K.Inomata and Y.Ukaji: "Development of the Asymmetric Cycloaddition Reactions and AsymmetricNucleophilic Addition Reaction Utilizing Tartaric Acid Esters" J.Synth.Org.Chem.Jpn,. 56. 11-21 (1998)

K.Inomata 和 Y.Ukaji：“利用酒石酸酯开发不对称环加成反应和不对称亲核加成反应”J.Synth.Org.Chem.Jpn,。