{"title":"Visible-light induced Mallory reaction of tertiary benzanilides via iminium intermediates","authors":"Xiaoqiang Ma, Si Wang, Zhanyong Tang, jialin Huang, Tianhao Jia, Xingda Zhao, Depeng Zhao","doi":"10.1039/d4sc03907f","DOIUrl":null,"url":null,"abstract":"The Mallory reaction is of significant synthetic importance, involving the photocyclization of stilbenes/diarylethenes and their analogues into polycyclic aromatics. However, the application of the Mallory reaction to tertiary benzanilides has not been explored to date. Besides, most of the reported Mallory reactions require ultraviolet irradiation. In this study, we show the first Mallory reaction of tertiary benzanilides promoted by visible-light via iminium intermediates formed in situ from tertiary benzanilide, Tf<small><sub>2</sub></small>O (triflic anhydride) and pyridine. UV/vis absorption spectroscopy combined with density functional theory (DFT) calculations revealed that the formation of the iminium intermiate decreased the HOMO-LUMO energy gap, thereby enhancing visible light absorption. This study provides a rapid and practical approach for preparation of phenanthridinone skeleton and also provides a new idea for design new visible light photoswitches.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":7.6000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc03907f","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Visible-light induced Mallory reaction of tertiary benzanilides via iminium intermediates
The Mallory reaction is of significant synthetic importance, involving the photocyclization of stilbenes/diarylethenes and their analogues into polycyclic aromatics. However, the application of the Mallory reaction to tertiary benzanilides has not been explored to date. Besides, most of the reported Mallory reactions require ultraviolet irradiation. In this study, we show the first Mallory reaction of tertiary benzanilides promoted by visible-light via iminium intermediates formed in situ from tertiary benzanilide, Tf2O (triflic anhydride) and pyridine. UV/vis absorption spectroscopy combined with density functional theory (DFT) calculations revealed that the formation of the iminium intermiate decreased the HOMO-LUMO energy gap, thereby enhancing visible light absorption. This study provides a rapid and practical approach for preparation of phenanthridinone skeleton and also provides a new idea for design new visible light photoswitches.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.