Organic Synthesis Using Electroauxiliaries

使用电助剂的有机合成

• 批准号: 07455360
• 负责人: YOSHIDA Jun-ichi
• 金额: $ 4.93万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07455360/
• 关键词: Electron Transfer; Organic Synthesis; Electrochemical Oxidation; 電子補助基; 電解; ケイ素; スズ; 電解還元

We propose a new concept of electroauxiliary as a useful tool in electron transfer-driven reactions. Electroauxiliaries activate reactant molecules to facilitate the electron transfer process and also control the chemical process of thus generated reactive species to give desired products selectively.We have found that silicon, tin, and sulfur serve as excellent electroauxiliaries for the oxidation of heteroatom compounds. The concept of electroauxiliary was found to be useful for oxidative carbon-carbon bond formation of heteroatom compounds. Several electrooxidative carbon-carbon bond formation reactions using tin and sulfur as electroauxiliaries have been developed.This concept was also found to be site-selective transformation of organic compounds because we can easily distinguish between electroauxiliaries at different sites of molecule using the difference of their redox potential.We also investigated the mechanism of the action of electroauxiliaries. In the case of silicon and tin, the electron transfer is accelerated by the interaction of the carbon-metal sigma orbital with the nonbonding porbital of the heteroatom which raises the HOMO level. In the case of sulfur, however, such interaction was not observed and the electron transfer was found to take place mainly from the sulfur atom.

我们提出了电辅助的新概念，作为电子转移驱动反应中的有用工具。电助剂活化反应物分子以促进电子转移过程，并控制由此产生的活性物质的化学过程以选择性地产生所需产物。我们发现硅、锡和硫是杂原子化合物氧化的优异电助剂。人们发现电辅助的概念对于杂原子化合物的氧化碳-碳键的形成是有用的。已经开发了几种使用锡和硫作为电助剂的电氧化碳-碳键形成反应。这个概念也被发现是有机化合物的位点选择性转化，因为我们可以利用氧化还原电位的差异轻松区分分子不同位点的电助剂。我们还研究了电助剂的作用机制。对于硅和锡，碳-金属西格玛轨道与杂原子非键合轨道的相互作用加速了电子转移，从而提高了 HOMO 能级。然而，在硫的情况下，没有观察到这种相互作用，并且发现电子转移主要发生在硫原子上。

项目成果

吉田潤一: "電子移動における14族元素のB効果とその有機電解合成への応用" 有機合成科学協会誌. 53. 53-63 (1995)

Junichi Yoshida：“第 14 族元素对电子转移的 B 效应及其在有机电合成中的应用”有机合成科学协会杂志 53. 53-63 (1995)。

Masanobu Sugawara: "Anodic Oxidation of Carbamates Using Organothio Groups as Electroauxiliaries" Electrochimica Acta in press.

Masanobu Sukawara：“使用有机硫基团作为电助剂的氨基甲酸酯的阳极氧化”《电化学学报》正在出版。

吉田潤一: "電子移動における14族元素のβ効果とその有機電解合成への応用" 有合化. 53. 53-63 (1995)

Junichi Yoshida：“14族元素对电子转移的β效应及其在有机电合成中的应用”Synthesis. 53. 53-63 (1995)。

Shigeru Yamago: "O-Glycosidation of Telluroglycosides by Electrochemical Oxidation" Chem.Lett.111-112 (1996)

Shigeru Yamago：“通过电化学氧化对碲糖苷进行 O-糖苷化”Chem.Lett.111-112 (1996)

Shigeru Yamago: "Practical Synthesis of Telluroglycosides" Synlett.929-930 (1996)

Shigeru Yamago：“碲糖苷的实用合成”Synlett.929-930 (1996)