Synthesis and some properties of alkynyl derivatives of 1,3-dialkylperimidones. An example of the 1,2-palladium migration in the Sonogashira reaction

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• 作者：Ekaterina A. Filatova ; Anna V. Gulevskaya ; ^{agulevskaya@sfedu.ru" class="auth_mail" title="E-mail the corresponding author} ; ^{anvasgul@gmail.com" class="auth_mail" title="E-mail the corresponding author} ; Alexander F. Pozharskii ; Valery A. Ozeryanskii
• 关键词：1 ; 3-Dialkyl-1H-perimidine-2(3H)-ones ; Alkynes ; Sonogashira coupling ; 1 ; 2-Palladium migration ; Thermal peri-cyclizations ; 3 ; 5-Diazadibenzo[cd ; k]fluoranthenes
• 刊名：Tetrahedron
• 出版年：2016
• 出版时间：24 March 2016
• 年：2016
• 卷：72
• 期：12
• 页码：1547-1557
• 全文大小：1533 K

文摘

A series of mono-, di-, tri- and tetra-alkynyl derivatives of 1,3-dimethyl- and 1,3-diethyl-1H-perimidine-2(3H)-ones have been obtained from the corresponding bromides via the Sonogashira reaction. It was found that placing two trimethylsilylethynyl groups into positions 6 and 7 (peri) of the perimidone makes a sterically hindered system and, sometimes, is accompanied by a previously unknown 1,2-migration of the Pd(II)-X group in the intermediate complex. Several peri-dialkynyl perimidones were tested for thermal or electrophile-initiated cyclizations resulting in the formation of some new polynuclear heterocyclic compounds, mostly derivatives of 3,5-diazadibenzo[cd,k]fluoranthene. The cyclizations have been found to proceed with more difficulty than those of 1,8-bis(phenylethynyl)naphthalene. This fact was ascribed to larger in-plane deformation of the naphthalene moiety in the perimidones that results in moving the peri-alkynyl groups apart from each other.