New Development of Asymmetric Olefination

不对称烯化新进展

• 批准号: 09672141
• 负责人: TANAKA Kiyoshi
• 金额: $ 2.05万
• 依托单位: University of Shizuoka (1998)Kyoto University (1997)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09672141/
• 关键词: Asymmetric reaction; HWE reaction; Chiral phosphonate; Diketone; MO calculation; Axial chirality; Intramolecular reaction; Chiral allenes; 不斉オレフィン化; H.W.E.反応; フォスフォネート試薬; 絶対構造; 速度論的支配; 軌道支配; 面斉不斉

The scientific research works of the asymmeric olefination, the research planning of which are described in the grant application form in detail, were performed and the following results are obtained.1. A variety of diketonic substrates were applied to the asymmetric olefination utilizing the axially chiral phosphonate reagent of the HWE type, and the general effectiveness of the reagent was positively proven. Therein, the absolute stereostructure of the products was determined by chemical transformations as well as the X-ray crystal analyses.2. The mechanistic aspects of the reaction was considered, where the kinetically controlled mechanism of the nucleophilic attack of the anion to the ketonic substrate as the rate determining step was proposed. The direction of the nucleophilic attack was estimated by using model experiments of thc Grignard reagents. From these model experiments and the calculation, it turned out that the direction was governed by the orbital control factors rather … More than the steric ones.3. A practical and efficient synthetic method based on the C-C bond formation was developed by using the BHT esters as the ketene equivalent. The new reaction system afforded the higher chemical and optical yield than the previously known method. In this study, it was shown that even the simple phenolic esters can be the precursor for the ketenes and gave the corresponding optically active allenic esters in satisfactory chemical and optical yield.4. The o-symmetrical diketones bearing the optically active phosphonate moiety were designed and prepared and intramolecular asymmetric HWE reaction based on the discrimination of the carbonyls was investigated. The optically active ring system having quaternary carbon and tetra-substituted olefinic moiety was successfully constructed in satisfactory chemical and optical yield. The absolute stereostructure of some of the products was unambiguously elucidated by the X-ray crystal analysis.5. The symmetrical metal (Fe and Cr) complexes of diene and arenes were applied as the substrates to the asymmetric olefination, and the corresponding olefinic products of the planar chirality was obtained in satisfactory chemical and optical yield.6. The preliminary experiments of the kinetic resolution of the racemic ketones was investigated. In the case of some amino acid derivatives, the high optical yield of the olefinic products was achieved and these extensive investigations are in progress. Less

开展了不对称烯化反应的科研工作，科研计划详见基金申请表，取得了以下成果.利用HWE型的轴向手性膦酸酯试剂，将各种双酮底物应用于不对称烯化反应，并积极证明了试剂的一般有效性。其中，通过化学转化和X射线晶体分析确定了产物的绝对立体结构。2.反应的机理方面被认为是，其中提出的动力学控制的机制的亲核攻击的阴离子的酮基底物的速率决定步骤。用格氏试剂的模型实验估计了亲核进攻的方向。通过模型实验和计算，发现其方向主要受轨道控制因子的影响 ...更多信息 而不是空间位阻的。以BHT酯类化合物为乙烯酮的等价物，发展了一种基于C-C键形成的合成方法。新的反应体系提供了更高的化学和光学产率比以前已知的方法。本研究表明，即使是简单的酚酯也可以作为烯酮的前体，并以令人满意的化学产率和光学产率得到相应的光学活性丙二烯酯.设计并合成了带有光学活性膦酸酯基团的邻位对称二酮，研究了基于羰基识别的分子内不对称HWE反应。以令人满意的化学产率和光学产率成功地构建了具有季碳和四取代烯基的光学活性环系统。通过X-射线晶体分析明确地阐明了某些产物的绝对立体结构.将对称金属（Fe和Cr）的二烯和芳烃配合物作为底物进行不对称烯化反应，得到了具有平面手性的相应烯烃产物，化学产率和光学产率都比较满意.对外消旋酮的动力学拆分进行了初步的实验研究。在某些氨基酸衍生物的情况下，烯烃产物的高光学产率已经实现，这些广泛的研究正在进行中。少

项目成果

Kiyoshi Tanaka, Toshiyuki Watanabe, Yoshihisa Ohta, and Kaoru Fuji: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in alpha-Diketones by a Chiral Phosphonate Reagent." Tetrahedron Letters. 38-52. 8943-894

Kiyoshi Tanaka、Toshiyuki Watanabe、Yoshihisa Ohta 和 Kaoru Fuji：“基于手性磷酸酯试剂对 α-二酮中对映羰基的辨别，形成非外消旋 E-和 Z-烯烃。”

田中 圭 他: "Use of 8, 8'-Dihydroxy-1, 1'-binaphthalene as a Chiral Auxiliary for Asymmetric Diels-Alder Cycloadditions" Tetrahedron : Asymmetry. 8. 3637-3645 (1997)

Kei Tanaka 等人：“使用 8, 8-二羟基-1, 1-联萘作为不对称狄尔斯-阿尔德环加成反应的手性助剂”四面体：不对称性 8. 3637-3645 (1997)。

田中 圭 他: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in α-Diketones by a Chiral Phosphonate Reagent" Tetrahedron Letters. 38.52. 8943-8946 (1997)

Kei Tanaka 等人：“通过手性磷酸酯试剂区分 α-二酮中的对映羰基形成非外消旋 E-和 Z-烯烃”Tetrahedron Letters 38.52 (1997)。

田中 圭 他: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in α-Diketones by a Chiral Phosphonate Reagent" Tetrahedron Letters. 38. 8943-8946 (1997)

Kei Tanaka 等人：“基于通过手性磷酸酯试剂区分 α-二酮中的对映羰基基团形成非外消旋 E-和 Z-烯烃”Tetrahedron Letters 38. 8943-8946 (1997)。

田中 圭 他: "光学活性リン試薬を用いる不斉オレフィン化" 有機合成化学協会誌. 56・6(印刷中). (1998)

Kei Tanaka 等人：“使用光学活性磷试剂的不对称烯化”有机合成化学学会杂志 56, 6（出版中）。