作者:Gabriela Mladenova、Gurmit Singh、Austin Acton、Lie Chen、Olga Rinco、Linda J. Johnston、Edward Lee-Ruff
DOI:10.1021/jo035439z
日期:2004.3.1
photochemical pinacol reaction of a series of nonsymmetrical 9-fluorenyl-substituted vic-diols was investigated and compared with their acid-catalyzed thermal reaction. Unlike the thermal reaction, the radiation-induced processes involve only fluorenyl cations, as is reflected in differences of product distribution between the two reactions. From the product studies, substituent migratory aptitudes are reversed
一系列不对称9-芴基-取代的频哪醇光化学反应VIC -diols进行了研究,并用它们的酸催化的热反应进行比较。与热反应不同,辐射诱导的过程仅涉及芴基阳离子,这反映在两个反应之间的产物分布差异上。根据产品研究,取代基的迁移能力在光化学过程中被逆转,这表明动力学控制是在中性条件下进行的,这与酸催化的热反应不同。芴基阳离子中间体的存在及其寿命是通过激光闪光光谱研究确定的。