Mogami Shunsuke, Baba Masanobu, Furuyama Taniyuki, Kunishima Munetaka, Mishiro Kenji
Faculty of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical, and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
Nanomaterial Research Institute, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
J Org Chem. 2024 Aug 2;89(15):10709-10718. doi: 10.1021/acs.joc.4c00947. Epub 2024 Jul 16.
This study developed reactions for the phototriggered generation of reactive ynol ethers using alkoxycyclopropenones. The resulting ynol ethers underwent rearrangement to ketenes, which subsequently participated in cycloaddition with alkynes and the acylation of amines. The alkoxy groups in the ynol ethers significantly influenced on the reactivity toward their rearrangement to ketenes. Reasonable transition state structures for the rearrangement reaction were found through density functional theory calculations, and the reactivity of the ynol ethers could be predicted by these calculations.
本研究利用烷氧基环丙烯酮开发了用于光触发生成反应性烯醇醚的反应。生成的烯醇醚发生重排生成烯酮，烯酮随后与炔烃发生环加成反应以及与胺发生酰化反应。烯醇醚中的烷氧基对其重排生成烯酮的反应活性有显著影响。通过密度泛函理论计算找到了重排反应合理的过渡态结构，并且这些计算可以预测烯醇醚的反应活性。
