Hashikawa Yoshifumi, Murata Yasujiro
Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan.
Chempluschem. 2021 Dec;86(12):1559-1562. doi: 10.1002/cplu.202100421. Epub 2021 Oct 11.
The partial zipping of a fullerene orifice was achieved by a water-mediated thermal rearrangement at 150 °C for one day while the orifice size changed from 16- to 14-membered ring with the generation of a fused pentagon. The addition of B(C F ) was found to facilitate the reaction likely due to the coordination to carbonyl groups on the orifice. By extending the reaction time, the decarbonylation took place to give another 14-membered-ring orifice where the Michael addition of water occurred under acidic conditions. The computational study suggested that the formation of a carboxylic acid and Fischer-type carbene plays a key role in the C-C bond cleavage/reformation processes during the rearrangement.
通过在150°C下进行水介导的热重排反应一天，实现了富勒烯孔口的部分拉链化，此时孔口尺寸从16元环变为14元环，并生成了一个稠合的五边形。发现添加B(CF)有助于该反应，这可能是由于其与孔口上的羰基配位。通过延长反应时间，发生脱羰反应，生成另一种14元环孔口，在此酸性条件下发生水的迈克尔加成反应。计算研究表明，羧酸和费歇尔型卡宾的形成在重排过程中的C-C键断裂/重新形成过程中起关键作用。
