{"title":"Divergent Radical, Dimerization, and Carbene Formation from One-Electron Reduction of 2-Cyanoimidazolium Salts","authors":"Jawon Jang, Jaelim Kim, Prof. Eunsung Lee","doi":"10.1002/ajoc.202500443","DOIUrl":null,"url":null,"abstract":"<p>Nitriles are indispensable synthetic building blocks for the construction of nitrogen-containing molecules with broad applications in pharmaceuticals, agrochemicals, and materials science. While their conventional two-electron reductions enable transformations into amines, carboxylic acids, and aldehydes, their one-electron reduction pathways, which lead to radical formation, remain largely unexplored. In this study, we report the rational synthesis of 2-cyanoimidazolium salts and investigate their one-electron reduction pathways. Upon reduction, these compounds yield both organic radicals and free carbenes. Notably, the free carbene formation occurs via electrophilic cyanide transfer proceeding through a mesoionic carbene (MIC) intermediate. We further demonstrate that the steric bulkiness of imidazolium N-substituents plays a critical role in determining radical stability. The imidazolium with a sterically bulky substituent generates the persistent radical, which is characterized by electron paramagnetic resonance (EPR) spectroscopy. In contrast, heating the radical with a less bulky N-substituent leads to dimerization, forming new C(sp)─C(sp<sup>2</sup>) and C(sp<sup>2</sup>)─N bonds. Insights into their mechanism are supported by density functional theory (DFT) calculations.</p>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 9","pages":""},"PeriodicalIF":2.7000,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Asian Journal of Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://aces.onlinelibrary.wiley.com/doi/10.1002/ajoc.202500443","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
Nitriles are indispensable synthetic building blocks for the construction of nitrogen-containing molecules with broad applications in pharmaceuticals, agrochemicals, and materials science. While their conventional two-electron reductions enable transformations into amines, carboxylic acids, and aldehydes, their one-electron reduction pathways, which lead to radical formation, remain largely unexplored. In this study, we report the rational synthesis of 2-cyanoimidazolium salts and investigate their one-electron reduction pathways. Upon reduction, these compounds yield both organic radicals and free carbenes. Notably, the free carbene formation occurs via electrophilic cyanide transfer proceeding through a mesoionic carbene (MIC) intermediate. We further demonstrate that the steric bulkiness of imidazolium N-substituents plays a critical role in determining radical stability. The imidazolium with a sterically bulky substituent generates the persistent radical, which is characterized by electron paramagnetic resonance (EPR) spectroscopy. In contrast, heating the radical with a less bulky N-substituent leads to dimerization, forming new C(sp)─C(sp2) and C(sp2)─N bonds. Insights into their mechanism are supported by density functional theory (DFT) calculations.
期刊介绍:
Organic chemistry is the fundamental science that stands at the heart of chemistry, biology, and materials science. Research in these areas is vigorous and truly international, with three major regions making almost equal contributions: America, Europe and Asia. Asia now has its own top international organic chemistry journal—the Asian Journal of Organic Chemistry (AsianJOC)
The AsianJOC is designed to be a top-ranked international research journal and publishes primary research as well as critical secondary information from authors across the world. The journal covers organic chemistry in its entirety. Authors and readers come from academia, the chemical industry, and government laboratories.