Department of Chemistry, University of Minnesota , 207 Pleasant Street, SE, Minneapolis, Minnesota 55455, United States.
J Am Chem Soc. 2017 Jun 28;139(25):8400-8403. doi: 10.1021/jacs.7b03832. Epub 2017 Jun 20.
We demonstrate that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction to produce reactive benzyne derivatives can be initiated photochemically. As with the thermal variant of the HDDA process, the reactive intermediates are formed in the absence of reagents or the resulting byproducts required for the generation of benzynes by traditional methods. This photo-HDDA (or hν-HDDA) reaction occurs at much lower temperatures (including even at -70 °C) than the thermal HDDA, but the benzynes produced behave in the same fashion with respect to their trapping reactions, suggesting they are of the same electronic state.
我们证明了可以通过光化学引发十六氢-Diels-Alder（HDDA）环化反应来生成反应性苯炔衍生物。与 HDDA 过程的热变体一样，在没有试剂或传统方法生成苯炔所需的副产物的情况下形成反应性中间体。这种光 HDDA（或 hν-HDDA）反应的温度比热 HDDA 低得多（甚至可以在-70°C 下进行），但生成的苯炔在其捕获反应方面表现出相同的行为，这表明它们处于相同的电子态。
