Activation of Olefins by Anodically Generated halogen Active Species and Its Application

阳极生成卤素活性物质活化烯烃及其应用

• 批准号: 03555182
• 负责人: MATSUMURA Yoshihiro
• 金额: $ 4.22万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555182/
• 关键词: Anodic oxidation; Olefin; Halogen; Iodine; Phenylacetic acid; ハロゲン活性種; 環状エナミン; 環縮小反応

Activation of olefins by oxidation using anodically generated halogen active species was studied, and the following reactions were exploited. 1.We have already found that the reaction of stirene derivatives with anodically generated iodine active species [I^+]/TMOF in trimethyl orthoformate (TMOF) gave phenylacetic acid derivatives. We found this time that TMOF was essential as a solvent or a co-solvent with methylene chloride, ethyl acetate, and so no for the formation of phenylacetic acid derivatives. 2.We found a new ring contraction reaction of cyclic amines by utilizing cyclic enamines prepared by anodic oxidation of cyclic amines. Also, [I^+]/TMOF was found to promote the ring contraction reaction. 3.A new method of the prepapration of beta-aryl-substituted cyclic amines was exploited. Namely, beta-haho-alpha-methoxylation of cyclic enamines, the alpha-arylation, and silver ion treatment of the products gave beta-aryl-substituted cyclic amines. By this method, alkaloids such as mesembrine were prepared. 4.Optically acitive 1-acetyl-2-methoxycarbonyl-5-tosylaminopiperidine, a key intermediate for the synthesis of slaflamine, was prepared from L-lysine by utilyzing anodic oxidation. 5.We succeeded in the introduction of oxo group into beta-position of cyclic amines, and could prepare delta-aminolevulinic acid. Exploitation of optically active halogen species and a ring contraction of cyclic enol ethers are remained to be carried out as important subjects of this study.

研究了利用阳极生成的卤素活性物种对烯烃的氧化活化，并进行了以下反应。1.我们已经发现，在原甲酸三甲酯(TMOF)中，苯乙烯类化合物与阳极生成的碘活性物种[I~(++)]/TMOF反应生成苯乙酸类化合物。这一次，我们发现TMOF作为溶剂或与二氯甲烷、乙酸乙酯等共溶剂对于苯乙酸衍生物的形成是必不可少的。2.利用环胺阳极氧化制备的环烯胺，发现了环胺的一种新的环收缩反应。此外，[i^+]/TMOF也促进了环的收缩反应。3.探索了一种制备β-芳基取代环胺的新方法。也就是说，环烯胺的β-HAHO-α-甲氧基化、α-芳基化和银离子处理得到了β-芳基取代的环胺。用这种方法制备了膜等生物碱。4.以L-赖氨酸为原料，采用阳极氧化法制备了合成斯莱明的关键中间体--光学活性1-acetyl-2-methoxycarbonyl-5-tosylaminopiperidine，。5.成功地将氧基引入环胺的β-位，合成了β-氨基乙酰丙酸。光学活性卤素的开发和环烯醇醚的环收缩仍是本研究的重要课题。

项目成果

Y.Matsumura: "Electro-organic reactions utilizing halogen mediators : Electrochemical oxidation of enol-type and enamine-type compounds" Bull.Electrochem.6. 89-94 (1990)

Y.Matsumura：“利用卤素介体的有机电反应：烯醇型和烯胺型化合物的电化学氧化”Bull.Electrochem.6。

Y.Matsumura: "A Convenient Route to b-Aryl-substituted Cyclic Enamines as Key Synthetic Intermediates of Sceletium and Amaryllidaceae Alkaloids" Tetrahedron. 49. 8503-8512 (1993)

Y.Matsumura：“将 b-芳基取代的环状烯胺作为 Sceletium 和石蒜科生物碱的关键合成中间体的便捷途径”四面体。

Y.Matsumura: "A Convenient Method for Introducing Oxo Group into the beta-Position of Cyclic Amines and Its Application to Synthesis of delta-Amiolevulinic Acid" Bull Chem.Soc.Jpn.67. 304-306 (1994)

Y.Matsumura：“将氧代基团引入环胺β位的简便方法及其在合成δ-氨基乙酰丙酸中的应用”Bull Chem.Soc.Jpn.67。

Yoshihiro Matsumura: "A Convenient Route to β-Aryl-substituted Cyclic Enamines as Key Synthetic Intermediates of Sceletium and Amaryllidaceae Alkaloids" Tetrahedron. 49. 8503-8512 (1993)

Yoshihiro Matsumura：“将 β-芳基取代的环状烯胺作为 Sceletium 和石蒜科生物碱的关键合成中间体的便捷途径”Tetrahedron，49。8503-8512 (1993)。

Y.Matsumura: "A Convenient Method for Introducing Oxo Group into the β-Position of Cyclic Amines and Its Application to Synthesis of δ-Aminolevulinic Acid" Bull.Chem.Soc.Jpn. 67. 304-306 (1994)

Y.Matsumura：“将氧代基引入环胺β位的简便方法及其在合成δ-氨基乙酰丙酸中的应用”Bull.Chem.Soc.Jpn 67. 304-306 (1994)