Chen Lei, De Bo Guillaume
Department of Chemistry, University of Manchester Manchester M13 9PL UK
Chem Sci. 2025 Apr 15;16(17):7104-7105. doi: 10.1039/d5sc90082d. eCollection 2025 Apr 30.
Symmetry-forbidden reactions are notoriously difficult to investigate as they are typically overshadowed by the corresponding symmetry-allowed pathway. Mechanical activation allows access to reaction pathways disfavoured using other methods of activation, such as the symmetry-forbidden disrotatory ring-opening of substituted -cyclobutenes. In a recent publication, Bowser, have studied the effects of various substituents on this reaction using atomic force microscopy and computational analysis (B. H. Bowser, C. L. Brown, J. Meisner, T. B. Kouznetsova, T. J. Martínez and S. L. Craig, , 2025, https://doi.org/10.1039/D5SC00253B). The largest effect is observed with substituents close to the scissile bond having the ability to stabilise the diradical character of the disrotatory ring-opening reaction pathway.
对称性禁阻反应因其通常被相应的对称性允许途径所掩盖而极难研究。机械活化能够开启通过其他活化方法难以实现的反应途径，例如取代环丁烯的对称性禁阻的顺旋开环反应。在最近的一篇论文中，鲍泽等人使用原子力显微镜和计算分析研究了各种取代基对该反应的影响（B. H. 鲍泽、C. L. 布朗、J. 迈斯纳、T. B. 库兹涅佐娃、T. J. 马丁内斯和S. L. 克雷格，《化学科学》，2025年，https://doi.org/10.1039/D5SC00253B）。当靠近可裂解键的取代基能够稳定顺旋开环反应途径的双自由基特性时，观察到的影响最大。
