Development of Five-membered Ring Forming Reactions by Control of Electronic States of Biradical

双自由基电子态控制五元环形成反应的发展

• 批准号: 05403015
• 负责人: NAKAMURA Eiichi
• 金额: $ 22.46万
• 依托单位: The University of Tokyo (1995)Tokyo Institute of Technology (1993-1994)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 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-05403015/
• 关键词: biradical; trimethylenemethane; vinglcarbene; pyrrolidine; five-membered rings; 付加環化反応; フラーレン; ラジカル; 超音波; 核酸切断; 反応機構; 抗ガン活性

Focusing on the possibility of controlling the electronic structures of biradical species, the investigator carried out a research on the [3+2] cycloaddition reaction to form five-membered rings. As the result, electronic control of the trimethylenemethane (TMM) and vinyl radical (VC) species has been achieved to generate new dipolar three-carbon, four-electron reactive species, and the reactions of these species with two-electron acceptors have been developed to realize new synthesis of five-membered ring compounds. The major achievements are summarized as follows.(1) Reactivity control of substituted TMM and VC species. By the use of the highly strained monocyclic rings, cyclopropene and methylenecyclopropane, the investigator performed kinetic studies on the TMM and VC formation reactions, and applied the results to the synthesis of cyclopentane and pyrollidine compounds. (2) Fullerene functionalization. TMM and VC have been found to react with fullerenes, and the results were applied for the studies various properties of water-soluble fullerenes including biological activities, monolayr formation, and synthesis of radioactive derivatives. (3) Ultrasound control of radical reactions. The ability of ultrasound irradiation for the control of radical reactions have been studied.

着眼于控制双自由基物种电子结构的可能性，研究者开展了[3+2]环加成反应形成五元环的研究。结果，实现了三亚甲基甲烷（TMM）和乙烯基自由基（VC）物种的电子控制，生成新的偶极三碳、四电子反应物种，并且开发了这些物种与双电子受体的反应实现五元环化合物的新合成。主要成果概括如下：(1)取代TMM和VC物种的反应性控制。利用高张力单环环丙烯和亚甲基环丙烷，研究人员对TMM和VC形成反应进行了动力学研究，并将结果应用于环戊烷和吡咯烷化合物的合成。 (2)富勒烯功能化。人们发现TMM和VC与富勒烯发生反应，并将结果应用于水溶性富勒烯的各种性质的研究，包括生物活性、单层形成和放射性衍生物的合成。 (3)自由基反应的超声控制。已经研究了超声辐射控制自由基反应的能力。

项目成果

S.Yamago: "A Concise Synthetic Route to Cyclopentenes by [3+2] Cycloaddition of Dipolar Trimethylenemethane to Acetylenes" Angew.Chem.34. 2154-2156 (1995)

S.Yamago：“通过[3 2]偶极三亚甲基甲烷与乙炔的环加成得到环戊烯的简明合成路线”Angew.Chem.34。

S.Yamago: "Synthesis and [2+2] Cycloaddition of Dimethyleneketene Acetals. Reaction with C60 and Facile Hydrolysis of the CC Bond Conected to C60" J.Am.Chem.Soc.116. 1123-1124 (1994)

S.Yamago：“二亚甲基乙烯酮缩醛的合成和 [2 2] 环加成。与 C60 的反应以及与 C60 连接的 CC 键的容易水解”J.Am.Chem.Soc.116。

E.Nakamura: "Synthetic Chemistry of Cyclopropenone Acetals. Penitricin and Buckminsterfullerene" Journal of Organic Chemistry, Japan. 52. 935-945 (1994)

E.Nakamura：“环丙烯酮缩醛的合成化学。青霉素和巴克敏斯特富勒烯”有机化学杂志，日本。

H.Tokuyama: "Regioselective Generation and Stereoselective[1+2]Cycloaddition of Vinylcarbenes" Synlett. 589-591 (1993)

H.Tokuyama：“乙烯基卡宾的区域选择性生成和立体选择性[1 2]环加成”Synlett。

S. Yamago: "A Concise Synthetic Route to Cyclopentenes by [3+2]Cycloaddition of Dipolar Trimethylenemethane to Acetylenes" Angew. Chem.34. 2154-2156 (1995)

S. Yamago：“通过偶极三亚甲基甲烷与乙炔的 [3 2]环加成反应生成环戊烯的简明合成路线”Angew。