Creation and Systematization of New Organic Cation Chemistry

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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.