Zakharov A V, Yadykov A V, Lvov A G, Mitina E A, Shirinian V Z
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russia.
Org Biomol Chem. 2020 Apr 29;18(16):3098-3103. doi: 10.1039/d0ob00296h.
A novel protocol for the synthesis of functionalized phenanthrenes through photocyclization of diarylethenes (DAE) under UV irradiation is proposed. The reaction proceeds through 6π-electrocyclization with the formation of a cyclic (closed) intermediate that undergoes a rearrangement affording unsymmetrical phenanthrenes in good yields. However, in contrast to benzene derivatives, the photocyclization of naphthalene diarylethenes proceeds more slowly, which is confirmed by DFT calculations. The transformation was performed on a 1 mmol scale. The scalability showed that the diarylethenes bearing oxazole, thiazole, pyrazole and imidazole as aryl moieties are more prone to photorearrangement and can be used in preparative organic synthesis.
提出了一种通过二芳基乙烯（DAE）在紫外光照射下进行光环化反应合成功能化菲的新方案。该反应通过6π-电环化反应进行，形成环状（闭合）中间体，该中间体经过重排，以良好的产率得到不对称菲。然而，与苯衍生物不同，萘二芳基乙烯的光环化反应进行得较慢，这一点得到了密度泛函理论（DFT）计算的证实。该转化反应在1 mmol规模上进行。可扩展性表明，带有恶唑、噻唑、吡唑和咪唑作为芳基部分的二芳基乙烯更容易发生光重排，可用于有机合成制备。
