Palladium-catalyzed annulation of 9-halophenanthrenes with alkynes: Synthesis, structural analysis, and properties of acephenanthrylene-based derivatives

En Chih Liu, Min Kuan Chen, Jen Yi Li, Yao Ting Wu

研究成果: Article

15 引文 斯高帕斯(Scopus)

摘要

The palladium-catalyzed annulation of 9-bromoand 9-chlorophenanthrenes with alkynes gave 4,5-disubstituted acephenanthrylenes in yields of 58-95% (9 examples). Asymmetric alkynes, such as 1-phenyl-1-propyne, 1-phenyl-1-hexyne, and 1-cyclopropyl-2-phenylethyne, regioselectively form (cyclo)alkyl-substituted products, following the regular rule that governs the carbopalladation of alkynes. This synthetic protocol can also be utilized in annulations with several p-extended bromoarenes, such as 7-bromo[5]helicene, 5-bromo[4]helicene, 9-bromoanthracene, 3-bromoperylene, and 3-bromofluoranthene, to give the corresponding annulated products in moderate to good yields (51-86%; 6 examples). Similarly, bromocorannulene produced highly curved 1,2-disubstituted cyclopentacorannulenes. Reactions of 6,12-dibromochrysene and 4,7-dibromo[4]helicene with di(4-tolyl) ethyne provided the twofold annulated products in moderate yields. 4,5-Diphenylacephenanthrylene and 6,7-diphenylbenzo[ a]acephenanthrylene thus generated were converted into phenanthro[9,10-e]acephenanthrylene and benzo[ a]phenanthro[9,10-e]acephenanthrylene, respectively, by oxidative cyclodehydrogenation. The structures of 4,5-diphenylacephenanthrylene, 4,5-diphenyldibenzo[a,l]acephenanthrylene, 1,2-diarylcyclopentacorannulenes, and benzo[ a]-phenanthro[9,10-e]acephenanthrylene were verified by X-ray crystallography. The photophysical and electrochemical properties of the selected annulated products were investigated.

原文English
頁(從 - 到)4755-4761
頁數7
期刊Chemistry - A European Journal
21
發行號12
DOIs
出版狀態Published - 2015 三月 16

    指紋

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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