Development and Application of Novel Asymmetric Carbon-Carbon Bond Forming Reactions

新型不对称碳-碳键形成反应的开发与应用

• 批准号: 13672224
• 负责人: TANAKA Kiyoshi
• 金额: $ 2.3万
• 依托单位: University of Shizuoka
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672224/
• 关键词: Asymmetric tandem reaction; One-flask reaction; Multiple asymmetric induction; Successive multi-component reaction; Asymmetric Michael reaction; Asymmetric olefination; Dynamic kinetic resolution; 多成分連続反応

Control of carbon skeleton including stereochemistry is a major factor for construction of useful and complex organic molecules. This study is involves in such a research work whose contents is development of novel and unique tantem carbon-carbon bond forming reactions of multi-components. The results and useful information obtained from this research work will be reviewed below.A combination of the Wittig and Michael reactions was designed for a new tandem reaction system and first function of two binaphthyl derivative was examined for effective substrate. A preliminary experiment of the asymmetric Michael reaction was carried out to give a high stereo(enantio) selectivity. Successively, the tandem Michael and HWE reaction was next tried using benzaldehyde as trapping substrate of the in situ generated carbanion giving the product with quite high enantioselectivity. This one-flask tandem reaction was successfully applied to double asymmetric induction. The ability of newly designed HWE reagent was investigated in three kinds of effective approaches for asymmetric olefination and the product formation with high both the chemical and optical yields was observed.Finally, the tandem asymmetric Michael-HWE system was efficiently applied to dynamic kinetic resolution to give the product in satisfactory chemical yield with high diastereo-selectivity.

碳骨架的控制包括立体化学是构建有用的和复杂的有机分子的主要因素。本研究就是开展这样一项研究工作，其内容是发展新颖独特的多组分碳-碳键形成反应。本文设计了一个新的Wittig反应和Michael反应的串联反应体系，并考察了两个联萘衍生物的第一功能作为有效底物。对不对称Michael反应进行了初步实验，得到了较高的立体（对映）选择性。接下来，尝试了串联Michael和HWE反应，使用苯甲醛作为原位生成的碳负离子的捕获底物，得到具有相当高的对映选择性的产物。这种一瓶串联反应被成功地应用于双重不对称诱导。考察了HWE试剂在三种有效的不对称烯化反应中的应用能力，发现HWE试剂均具有较高的化学产率和光学产率，并将其应用于动态动力学拆分，得到了较高的化学产率和非对映选择性。

项目成果

K.Tanaka., et al.: "Asymmetric construction of novel bicyclo[4. 4. 0]and [4. 3. 0]ring systems via intramolecular Horner-Wadsworth-Emmons reactions"Tetrahedron: Asymmetry. 13. 729-734 (2002)

K.Tanaka. 等人：“通过分子内 Horner-Wadsworth-Emmons 反应不对称构建新型双环 [4. 4. 0] 和 [4. 3. 0] 环系统”四面体：不对称性。

田中 圭他: "Asymmetric construction of novel bicyclo [4.4.0] and [4.3.0] ring systems via intramolecular Horner-Wadsworth-Emmons reactions"Tetrahedron : Asymmetry. 13. 729-734 (2002)

Kei Tanaka 等人：“通过分子内 Horner-Wadsworth-Emmons 反应构建新型双环 [4.4.0] 和 [4.3.0] 环系统”Tetrahedron：Asymmetry 13. 729-734 (2002)。

K.Tanaka., et al.: "Use of meso-ternaphthlene derivatives: linear recognition of α, ω-diamines by homoditopic receptors"Tetrahedron: Asymmetry. 58. 5611-5617 (2002)

K.Tanaka.等人：“内消旋四萘衍生物的使用：同二位受体对α，ω-二胺的线性识别”Tetrahedron：Asymmetry 58. 5611-5617 (2002)

田中 圭 他: "Intramolecular asymmetric olefination of binaphthyl phosphonate derivatives of 1,3-diketones"Tetrahedron : Asymmetry. 13(in press). (2002)

Kei Tanaka 等人：“1,3-二酮二萘基膦酸酯衍生物的分子内不对称烯化”四面体：不对称性 13（出版中）。