Ozaki Tomoya, Bentley Sierra K, Rybansky Nina, Li Bo, Liu Shih-Yuan
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.
J Am Chem Soc. 2024 Sep 11;146(36):24748-24753. doi: 10.1021/jacs.4c08088. Epub 2024 Jul 31.
The synthesis and crystallographic characterization of BN-benzvalene, the first second-row heteroatom-containing benzvalene, is described. BN-benzvalenes are produced via photoexcitation of C5-aryl-substituted 1,2-azaborines under flow conditions. Mechanistic studies support a boron-specific, two-step photoisomerization pathway involving a BN-Dewar benzene intermediate, which is distinct from the photoisomerization pathway proposed in benzene and phospha- and silabenzenes for the formation of their respective benzvalene analogues.
本文描述了首个含第二周期杂原子的苯并戊搭烯——BN-苯并戊搭烯的合成及晶体学表征。BN-苯并戊搭烯是在流动条件下通过对C5-芳基取代的1,2-氮杂硼苯进行光激发制备的。机理研究支持了一种特定于硼的两步光异构化途径，该途径涉及BN-杜瓦苯中间体，这与苯以及磷苯和硅苯中提出的用于形成各自苯并戊搭烯类似物的光异构化途径不同。
