Department of Chemistry, Oklahoma State University , Stillwater, Oklahoma 74078, United States.
J Am Chem Soc. 2014 Apr 9;136(14):5275-8. doi: 10.1021/ja5019749. Epub 2014 Mar 28.
Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.
最近，人们对热力学上不太稳定的 Z-烯烃的催化方法产生了浓厚的兴趣。这些方法依赖于对反应的动力学控制来获得热力学上不太稳定的几何异构体。在此，我们提出了一种正交的方法，通过光化学催化 E-烯烃异构化为热力学上不太稳定的 Z-异构体来实现，该异构化过程是通过光化学泵浦机制进行的。我们考虑了两种潜在的机制。重要的是，反应条件温和、耐受，操作简单，易于实施。
