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

Research output: Contribution to journalArticle

15 Citations (Scopus)

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-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.

Original languageEnglish
Pages (from-to)4755-4761
Number of pages7
JournalChemistry - A European Journal
Volume21
Issue number12
DOIs
Publication statusPublished - 2015 Mar 16

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Alkynes
X ray crystallography
Palladium
Electrochemical properties
Structural analysis
Structural properties
Derivatives
Acetylene
acephenanthrylene
3,4-10,11-12,13-tribenzofluoranthene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

@article{1a56be31fc1449e09d12738b78a243a1,
title = "Palladium-catalyzed annulation of 9-halophenanthrenes with alkynes: Synthesis, structural analysis, and properties of acephenanthrylene-based derivatives",
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-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.",
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Palladium-catalyzed annulation of 9-halophenanthrenes with alkynes : Synthesis, structural analysis, and properties of acephenanthrylene-based derivatives. / Liu, En Chih; Chen, Min Kuan; Li, Jen Yi; Wu, Yao Ting.

In: Chemistry - A European Journal, Vol. 21, No. 12, 16.03.2015, p. 4755-4761.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Palladium-catalyzed annulation of 9-halophenanthrenes with alkynes

T2 - Synthesis, structural analysis, and properties of acephenanthrylene-based derivatives

AU - Liu, En Chih

AU - Chen, Min Kuan

AU - Li, Jen Yi

AU - Wu, Yao Ting

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N2 - 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.

AB - 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.

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