Creation and Systematization of New Organic Cation Chemistry

本研究旨在利用阳离子池法深化有机阳离子的化学，即在没有亲核试剂的情况下，通过有机化合物的低温电化学氧化来生成和积累有机阳离子。研究了N-酰亚胺离子和烷氧基卡宾离子等有机阳离子的稳定性和反应活性，并设计和开发了几个新的反应。有机阳离子的结构和稳定性基于阳离子池法对有机阳离子进行了核磁共振研究。并研究了其热稳定性与阳离子结构的关系。有机阳离子的合成应用。通过阳离子池法产生各种有机阳离子并用于合成反应。例如，二芳基卡宾离子池是通过阳极氧化二芳基甲烷的氧化C-H键解离而产生的。ArS(ArSSAr)+由ArSSAr电化学生成，用于合成有机硫化合物。此外，利用Ars(ArSSAr)+与硫代缩醛的反应，建立了一锅间接生成烷氧基卡宾离子池的方法。还发展了Ars(ArSSAr)+引发的分子内碳-碳键形成的链式反应。此外，还发展了N-酰亚胺离子池与苯基硅烷的偶联，这种偶联是通过氧化C-Si键断裂的链机制进行的。本研究结果为有机阳离子的化学增添了新的维度。

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.