Singh Hemant K, Kaźmierski Sławomir, Kaszyński Piotr
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Łódź, Poland.
Faculty of Chemistry, University of Łódź, 91-403 Łódź, Poland.
J Org Chem. 2025 Jul 11;90(27):9425-9430. doi: 10.1021/acs.joc.5c00741. Epub 2025 Jun 27.
The recent discovery of a photo-Smiles rearrangement and the development of effective analytical methods prompted structural investigation of the previously reported planar Blatter radicals obtained by photocyclization of 8-aryloxy-3-phenylbenzo[][1,2,4]triazines. Thus, seven freshly prepared radicals were cleanly converted to their forms and analyzed by 2D correlation H NMR methods (COSY, TOCSY, and ROSEY). Results demonstrate that all investigated 8-aryloxy-3-phenylbenzo[][1,2,4]triazines undergo photocyclization with Smiles rearrangement and exclusive formation of a single rearranged product. This work corrects the previously reported structural assignment and DFT data of planar Blatter radicals and further demonstrates the generality of this new variation of the photo-Smiles rearrangement.
最近光致斯迈尔斯重排的发现以及有效分析方法的发展促使对先前报道的通过8-芳氧基-3-苯基苯并[][1,2,4]三嗪光环化得到的平面布拉特自由基进行结构研究。因此，七个新制备的自由基被顺利转化为它们的形式，并通过二维相关氢核磁共振方法（COSY、TOCSY和ROSEY）进行分析。结果表明，所有研究的8-芳氧基-3-苯基苯并[][1,2,4]三嗪都经历了伴有斯迈尔斯重排的光环化反应，并唯一形成单一的重排产物。这项工作纠正了先前报道的平面布拉特自由基的结构归属和密度泛函理论数据，并进一步证明了这种光致斯迈尔斯重排新变体的普遍性。
