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Creation and Systematization of New Organic Cation Chemistry

新有机阳离子化学的创造和系统化

基本信息

批准号：
17205012
负责人：
YOSHIDA Jun-ichi
金额：
$ 31.95万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17205012/
关键词：
organic cations cation pool method reactivity stability N-acyliminium ions alkoxycarbenium ions diarylcarbenium ions cationic organosulfur compounds フロー系反応装置

项目摘要

The present study was aimed at deepening the chemistry of organic cations using the cation pool method, which involved the generation and accumulation of organic cations by low temperature electrochemical oxidation of organic compounds in the absence of nucleophiles. The stability and reactivity of the organic cations such as N-acyliminium ions and alkoxycarbenium ions were studied, and several reactions were newly designed and developed.1. Structures and stability of organic cationsNMR studies on organic cations were carried out based on the cation pool method. The relationship between thermal stability and cation structures was also studied.2. Synthetic applications of organic cations.Various organic cations were generated by the cation pool method and used for synthetic reactions. For example, diarylcarbenium ion pools were generated by the oxidative C-H bond dissociation of diarylmethanes using anodic oxidation. ArS (ArSSAr) + was generated electrochemically from ArSSAr and was used for the synthesis of organosulfur compounds. In addition, a sequential one-pot indirect method for the generation of alkoxycarbenium ion pools was developed using the reaction of ArS (ArSSAr) + with a thioacetal. An ArS (ArSSAr) +-initiated chain reaction involving intramolecular carbon-carbon bond formation was also developed. And furthermore, coupling of an N-acyliminium ion pool with a benzylsilane, which proceeded by a chain mechanism involving oxidative C-Si bond cleavage, was developed.The results obtained in the present research add a new dimension of the chemistry of organic cations.

本研究的目的是深化有机阳离子的化学使用阳离子池方法，其中涉及的有机化合物在没有亲核试剂的低温电化学氧化的有机阳离子的产生和积累。研究了有机阳离子如N-酰基正离子和烷氧碳正离子的稳定性和反应活性，并设计和开发了几个新的反应.有机阳离子的结构与稳定性利用阳离子池法对有机阳离子进行了核磁共振研究。研究了阳离子结构与热稳定性的关系.有机阳离子的合成应用。通过阳离子池方法产生各种有机阳离子，并用于合成反应。例如，通过使用阳极氧化使二芳基甲烷氧化C-H键解离来产生二芳基碳鎓离子池。ArS（ArSSAr）+由ArSSAr电化学生成，并用于有机硫化合物的合成。此外，一个顺序的一锅间接的方法产生的烷氧基碳正离子池的开发使用的反应ArS（ArSSAr）+与硫缩醛。一个ArS（ArSSAr）+引发的链反应，涉及分子内的碳-碳键的形成也被开发。此外，还发展了N-酰基咪唑离子池与苄基硅烷的偶联反应，该偶联反应是通过C-Si键氧化断裂的链式机理进行的，为有机阳离子化学的研究增添了新的内容。