Lvov Andrey G, Shirinian Valerii Z, Zakharov Alexey V, Krayushkin Mikhail M, Kachala Vadim V, Zavarzin Igor V
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences , 47, Leninsky prosp., 119991 Moscow, Russian Federation.
J Org Chem. 2015 Nov 20;80(22):11491-500. doi: 10.1021/acs.joc.5b02237. Epub 2015 Nov 11.
A novel and efficient photochemical transformation of diarylethenes comprising a five-membered heterocyclic ring and phenyl moiety is described. This reaction provides a simple method for the preparation of functionalized naphthalene derivatives via photorearrangement reaction of diarylethenes, and the process is characterized by high efficiency that was determined by NMR monitoring. Some mechanistic aspects of this process have been also explored. It was found that the reaction includes tandem transformation of three basic processes: the photocyclization of the hexatriene system, [1,9]-sigmatropic rearrangement, and heterocyclic ring opening. Diarylethenes with different heterocycle moieties (thiophene, benzo[b]thiophene, furan, indole, imidazole, thiazole, oxazole, pyrazole) have been involved into this process, and the target naphthalenes with good yields have been obtained. The opportunity for use in the transformation of diarylethenes with different heterocyclic residues permits synthesis of naphthalenes with desired functional groups. The general character and high efficiency of the reaction promise that the transformation can be an effective synthetic route for the annulation of benzene rings to various aromatic systems, including heterocycles.
描述了一种新型且高效的包含五元杂环和苯基部分的二芳基乙烯的光化学转化反应。该反应通过二芳基乙烯的光重排反应提供了一种制备官能化萘衍生物的简便方法，并且该过程具有通过核磁共振监测确定的高效率的特征。还探索了该过程的一些机理方面。发现该反应包括三个基本过程的串联转化：己三烯体系的光环化、[1,9]-σ迁移重排和杂环开环。具有不同杂环部分（噻吩、苯并[b]噻吩、呋喃、吲哚、咪唑、噻唑、恶唑、吡唑）的二芳基乙烯参与了该过程，并获得了高产率的目标萘。使用具有不同杂环残基的二芳基乙烯进行转化的机会允许合成具有所需官能团的萘。该反应的普遍性和高效率表明，该转化可以成为将苯环环合到各种芳香体系（包括杂环）的有效合成路线。
