Abstract

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 7-5] helicene, 5- 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 4,7-4] 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

Department(s)

Chemistry

Document Type

Article - Journal

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Citation

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text

Language(s)

English

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© 2025 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, all rights reserved

Publication Date

2015

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