Umpolung of Organometallic Compounds by Electrochemical Reactions and Its Applications to Carbon-Carbon Bond Formation

有机金属化合物的电化学反应反极性及其在碳-碳键形成中的应用

• 批准号: 04640511
• 负责人: YOSHIDA Jun-ichi
• 金额: $ 1.28万
• 依托单位: OSAKA CITY UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640511/
• 关键词: Electrochemical Reaction; Organotin Compounds; Carbon-Carbon Bond Formation; Organofluorine Compounds; 有機ケイ素化合物; 電極酸化反応

We have found that anodic oxidation of alpha-heteroatom-substituted organotin compounds results in the cleavage of the C-Sn bond and the introduction of a nucleophile onto the carbon. Therefore, the electrochemical oxidation provides an efficient method for"umpolung"of organotion compounds.On the basis of this reaction we have developed intermolecular and intramolecular carbon-carbon bond formation reactions which provide useful tools in organic synthesis.For example, the anodic oxidation of alpha-stannyl ethers and carbamates containing carbon-carbon double bonds lead to effective cyclization. A fluorine atom is introduced onto one of the original olefinic carbons in the cyclized product, indicationg that fluoride ion from Bu_4NBF_4 (supporting electrolyte) attacked the cyclized cation as nucleophile. Bu_4NPF_6 was also found to be effective as the fluoride source. The present method is generally applicable to endo cyclization to form six- and seven-membered rings. Endo cyclization to form a five-membered ring was not successful. The methord outlined here is a new approach to both electrochemical carbon-carbon bond formation and the synthesis of fluorine-containing compounds.We have also developed an intermolecular carbon-carbon bond formation. The anodic oxidation of alpha-heteroatom substituted organotin compounds in the presence of allylsilanes or silyl enol ethers as carbon nucleophiles also proceeds smoothly to give the corresponding coupling products.The reactions we have developed in this project provide new aspects of organometallic chemistry and electro-organic chemistry.

我们已经发现，α-杂原子取代的有机锡化合物的阳极氧化导致C-Sn键的断裂和亲核试剂在碳上的引入。在此基础上，我们发展了分子间和分子内碳碳键形成反应，为有机合成提供了有用的工具，如α-锡烷基醚和氨基甲酸酯的阳极氧化可有效地进行环化反应。环化产物中的一个烯碳上引入了一个氟原子，表明来自Bu_4NBF_4（支持电解质）的氟离子作为亲核试剂进攻环化阳离子。Bu_4NPF_6也是一种有效的氟源。本方法通常适用于内环化形成六元环和七元环。形成五元环的内切环化不成功。本文介绍的方法为电化学碳-碳键的形成和含氟化合物的合成开辟了一条新的途径，并发展了分子间碳-碳键的形成。α-杂原子取代的有机锡化合物在烯丙基硅烷或烯醇醚为碳亲核试剂存在下的阳极氧化反应也顺利进行，得到相应的偶联产物，我们在本项目中发展的反应为有机金属化学和有机电化学提供了新的方面。

项目成果

Jun-ichi Yoshida, Masanori Itoh, and Sachihiko Isoe: "Electrooxidative Coupling of alpha-Heteroatom-substituted Organostannanes and Organosilanes" J.Chem.Soc., Chem.Commun.547 (1993)

Jun-ichi Yoshida、Masanori Itoh 和 Sachihiko Isoe：“α-杂原子取代的有机锡烷和有机硅烷的电氧化偶联”J.Chem.Soc.，Chem.Commun.547 (1993)

Jun-ichi Yoshida, Yuji Ishichi, and Sachihiko Isoe: "Introamolecular Carbon-Carbon Bond Formation by the Anodic Oxidation of Unsaturated alpha-Stannyl Heteroatom Compounds, Synthesis of Fluorine-Containig Hetero-cyclic Compounds" J.Am.Chem.Soc.114. 7594 (

Jun-ichi Yoshida、Yuji Ishichi 和 Sachihiko Isoe：“通过不饱和 α-甲锡烷基杂原子化合物的阳极氧化形成分子内碳-碳键，含氟杂环化合物的合成”J.Am.Chem.Soc.114

吉田・石地・西脇・磯江: "Electrochemical Oxidation of alpha-Alkoxystannanes." Tetrahedron Lett.33. 2599-1603 (1992)

Yoshida、Ishiji、Nishiwaki 和 Isoe：“α-烷氧基锡烷的电化学氧化”。33 2599-1603 (1992)。

吉田、伊藤、磯江: "Electrooxidative Coupling of α-Heteroatom-substituted Organostannanes and Organosilanes" J.Chem.Soc.,Chem.Commun.547-549 (1993)

Yoshida、Ito、Isoe：“α-杂原子取代的有机锡烷和有机硅烷的电氧化偶联”J.Chem.Soc.、Chem.Commun.547-549 (1993)

Jun-ichi Yosida, Yuji Ishichi, Keiji Nishiwaki, Satoshi Shiozawa, and Sachihiko Isoe: "Electrochemical Oxidation of alpha-Alkoxystannanes." Tetrahedron Lett.33. 2599 (1992)

Jun-ichi Yosida、Yuji Ishichi、Keiji Nishiwaki、Satoshi Shiozawa 和 Sachihiko Isoe：“α-烷氧基锡烷的电化学氧化”。