Revisit of the Dessy-White intramolecular acetylene-acetylene [2+2] cycloadditions
Revisit of the Dessy-White intramolecular acetylene-acetylene [2+2] cycloadditions
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DOI：
10.1021/jo061334v
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发表时间：
2006-10-27
影响因子：
3.6
通讯作者：
Peng, Shie-Ming
中科院分区：
文献类型：
--
作者：
Lee, Chung-Chieh;Leung, Man-kit;Peng, Shie-Ming
在该实验中，4,4'-二取代的2,2'-双(苯基乙炔基)联苯与2,3,4,5-四苯基环戊-2,4-二烯酮在纯净条件下在二苯醚中于260至270℃之间进行一系列热反应，产生9,10,11,12,13,14-六苯基环辛[1]菲作为加合物，产率为12-23%。我们将这些结果追溯到2,2'-双(苯基乙炔基)联苯的分子内[2+2]热环化形成1,2-二苯基环丁[1]菲，其进一步作为桥酮狄尔斯-阿尔德加合物被捕获，随后热脱羰开环，从而产生产物。
In this experiment, a series of thermal reactions of 4,4'-disubstituted 2,2'-bis( phenylethynyl) biphenyls with 2,3,4,5-tetraphenylcyclopenta-2,4-dienone were carried out under neat conditions and in diphenyl ether at temperatures between 260 and 270 degrees C to give rise to 9,10,11,12,13,14-hexaphenylcycloocta[1]phenanthrenes as the adducts in 12-23% yields. We traced these results to the intramolecular [2+2] thermal cyclization of 2,2'-bis(phenylethynyl) biphenyls to form 1,2-diphenylcyclobuta[1]phenanthrenes, which were further trapped as bridged-ketone Diels-Alder adducts, followed by thermal decarbonylative ring opening, which gave rise to the products.