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Synlett 2014; 25(11): 1585-1590
DOI: 10.1055/s-0033-1341282
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 1,2-Disubstituted Acenaphthylenes by Palladium-Catalyzed Annulation Reactions of Dibromoarenes with Internal Alkynes

Wenbo An
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China   Fax: +86(29)85300810   Email: gqli@snnu.edu.cn   Email: fengxu@snnu.edu.cn
,
Gaoqiang Li*
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China   Fax: +86(29)85300810   Email: gqli@snnu.edu.cn   Email: fengxu@snnu.edu.cn
,
Jun Ma
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China   Fax: +86(29)85300810   Email: gqli@snnu.edu.cn   Email: fengxu@snnu.edu.cn
,
Youping Tian
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China   Fax: +86(29)85300810   Email: gqli@snnu.edu.cn   Email: fengxu@snnu.edu.cn
,
Feng Xu*
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. of China   Fax: +86(29)85300810   Email: gqli@snnu.edu.cn   Email: fengxu@snnu.edu.cn
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Further Information

Publication History

Received: 11 March 2014

Accepted after revision: 07 April 2014

Publication Date:
08 May 2014 (online)

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Abstract

A simple and versatile route to 1,2-disubstituted acenaphthylenes has been developed. The method involves palladium-catalyzed annulation of 1,8-dibromonaphthalene or 5,6-dibromoacenaphthylene with an internal alkyne, and does not require any organometallic reagent. A range of 1,2-disubstituted acenaphthylenes and 5,6-disubstituted 1,2-dihydrocyclopenta[f,g]acenaphthylenes were prepared in moderate to good yields. The method provides a rapid and simple route to dibenzo[j,l]fluoranthene through an ­Ullmann coupling.

Key words

arenes - polycycles - annulations - cross-coupling - domino reactions

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References and Notes


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  • 15 1,2-Disubstituted Acenaphthylenes 3a–p; General Procedure A Schlenk flask was charged with dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%), Xantphos (5.5 mol%) and K2CO3 (1.5 mmol) under N2. Anhyd DMF (5 mL) was added from a syringe, and the mixture was stirred at 120 °C until the reaction was complete (TLC). The mixture was cooled to r.t., and H2O (10 mL) was added. The resulting mixture was extracted with EtOAc (3 × 15 mL). The organic layers were combined, dried (Na2SO4), and concentrated to give a residue that was purified by column chromatography (silica gel, PE–EtOAc). Methyl 4-(2-phenylacenaphthylen-1-yl)benzoate (3b) Orange solid; yield: 125 mg (69%); mp 166–167 °C. 1H NMR (300 MHz, CDCl3): δ = 8.03 (d, J = 8.3 Hz, 2 H), 7.88 (dd, J = 8.0, 2.2 Hz, 2 H), 7.73–7.78 (m, 2 H), 7.59–7.64 (m, 2 H), 7.51 (d, J = 8.3 Hz, 2 H), 7.35–7.43 (m, 5 H), 3.93 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 167.1, 140.3, 139.7, 139.6, 139.4, 136.9, 134.8, 130.0, 129.7, 128.6, 128.6, 128.3, 127.9, 127.9, 127.8, 127.6, 127.5, 124.5, 124.0, 52.1. HRMS (EI): m/z calcd for C26H18O2: 362.1307; found: 362.1305. 1-(4-Chlorophenyl)-2-phenylacenaphthylene (3c) Orange solid; yield: 125 mg (74%); mp 122–123 °C. 1H NMR (300 MHz, CDCl3): δ = 7.87 (d, J = 8.1 Hz, 2 H), 7.72 (dd, J = 10.9, 6.9 Hz, 2 H), 7.58–7.63 (m, 2 H), 7.31–7.44 (m, 9 H). 13C NMR (75 MHz, CDCl3): δ = 157.2, 139.8, 139.6, 138.7, 136.8, 135.0, 133.8, 133.1, 131.4, 130.1, 128.7, 128.6, 128.2, 127.9, 127.9, 127.6, 127.5, 127.4, 124.3, 123.8. HRMS (EI): m/z calcd for C24H15Cl: 338.0862; found: 338.0862. 1,2-Bis(2-chlorophenyl)acenaphthylene (3d) Yellow solid; yield: 121 mg (65%); mp 152–154 °C. 1H NMR (400 MHz, CDCl3): δ = 7.85–7.88 (m, 2 H), 7.54–7.62 (m, 4 H), 7.41–7.45 (m, 2 H), 7.28 (ddd, J = 10.1, 4.8, 2.7 Hz, 3 H), 7.25–7.15 (m, 3 H). 13C NMR (101 MHz, CDCl3): δ = 139.3, 138.7, 138.1, 134.5, 134.1, 134.1, 133.8, 132.1, 132.1, 130.2, 129.5, 129.0, 128.8, 128.5, 128.0, 127.7, 127.7, 127.6, 127.6, 126.7, 126.3, 124.7, 124.5. HRMS (EI): m/z calcd for C24H14Cl2: 372.0473; found: 362.0477. 1,2-Bis(4-tert-butylphenyl)acenaphthylene (3e) Orange solid; yield: 172 mg (83%); mp 164–165 °C. 1H NMR (300 MHz, CDCl3): δ = 7.83 (d, J = 8.1 Hz, 2 H), 7.75 (d, J = 6.8 Hz, 2 H), 7.54–7.59 (m, 2 H), 7.35–7.42 (m, 8 H), 1.36 (s, 18 H). 13C NMR (75 MHz, CDCl3): δ = 149.9, 140.4, 137.6, 132.4, 129.7, 128.3, 128.3, 127.7, 127.0, 125.2, 123.9, 34.6, 31.4. HRMS (EI): m/z calcd for C32H32: 416.2504; found: 416.2507. 1-Mesityl-2-phenylacenaphthylene (3f) Yellow oil; yield: 52 mg (30%). 1H NMR (400 MHz, CDCl3): δ = 7.80–7.85 (m, 3 H), 7.60 (dd, J = 8.0, 7.1 Hz, 1 H), 7.50 (dd, J = 8.1, 6.9 Hz, 1 H), 7.37–7.39 (m, 2 H), 7.27–7.32 (m, 3 H), 7.24 (d, J = 2.6 Hz, 1 H), 6.91 (s, 2 H), 2.33 (s, 3 H), 2.03 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ = 140.4, 139.9, 138.4, 138.2, 137.1, 136.8, 135.8, 131.5, 128.7, 128.4, 128.3, 128.2, 127.9, 127.6, 127.0, 127.0, 123.7, 123.2, 21.2, 20.6. HRMS (EI): m/z calcd for C27H22: 346.1722; found: 346.1720. 1-(4-Ethylphenyl)-2-phenylacenaphthylene (3g) Orange oil; yield: 114 mg (69%). 1H NMR (400 MHz, CDCl3): δ = 7.83 (dd, J = 8.1, 2.3 Hz, 2 H), 7.73 (dd, J = 14.9, 6.8 Hz, 2 H), 7.55–7.59 (m, 2 H), 7.44–7.46 (m, 2 H), 7.34–7.38 (m, 4 H), 7.29–7.31 (m, 1 H), 7.18 (d, J = 8.2 Hz, 2 H), 2.68 (q, J = 7.6 Hz, 2 H), 1.27 (t, J = 7.6 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 143.2, 140.2, 140.1, 138.2, 137.7, 135.5, 132.5, 130.1, 130.0, 128.4, 128.4, 128.3, 127.9, 127.8, 127.2, 127.1, 127.0, 124.1, 123.8, 28.7, 15.3. HRMS (EI): m/z calcd for C26H20: 332.1565; found: 332.1567. 1-Butyl-2-phenylacenaphthylene (3h) Yellow oil; yield: 109 mg (77%). 1H NMR (400 MHz, CDCl3): δ = 7.69–7.79 (m, 3 H), 7.51–7.58 (m, 7 H), 7.36–7.49 (m, 1 H), 2.87 (t, J = 7.6 Hz, 2 H), 1.75 (t, J = 7.6 Hz, 2 H), 1.42 (dd, J = 14.8, 7.4 Hz, 2 H), 0.91 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 140.7, 139.9, 137.9, 135.8, 129.6, 128.5, 128.5, 128.2, 127.7, 127.7, 127.1, 126.9, 126.4, 122.6, 122.4, 33.6, 26.1, 23.1, 14.0. HRMS (EI): m/z calcd for C22H20: 284.1565; found: 284.1566. 1-Phenyl-2-propylacenaphthylene (3i) Yellow oil; yield: 112 mg (83%). 1H NMR (400 MHz, CDCl3): δ = 7.69–7.79 (m, 3 H), 7.47–7.58 (m, 7 H), 7.38 (t, J = 7.2 Hz, 1 H), 2.84 (t, J = 7.2 Hz, 2 H), 1.76–1.82 (m, 2 H), 1.00 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 140.6, 140.6, 139.6, 138.0, 135.7, 129.5, 128.4, 128.3, 128.1, 127.7, 127.6, 127.0, 126.9, 126.4, 122.6, 122.3, 28.4, 24.6, 14.5. HRMS (EI): m/z calcd for C21H18: 270.1409; found: 270.1410. 5,6-Bis(4-tert-butylphenyl)-1,2-dihydrocyclopenta-[f,g]acenaphthylene (3l) Orange solid; yield: 170 mg (77%); mp 170–171 °C. 1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 7.0 Hz, 2 H), 7.46–7.48 (m, 4 H), 7.42 (d, J = 7.0 Hz, 2 H), 7.36–7.38 (m, 4 H), 3.52 (s, 4 H), 1.36 (s, 18 H). 13C NMR (101 MHz, CDCl3): δ = 149.6, 146.5, 137.1, 136.2, 135.3, 133.5, 129.6, 127.0, 126.0, 125.2, 120.7, 34.6, 32.6, 31.4. HRMS (EI): m/z calcd for C34H34: 442.2661; found: 442.2658. 5,6-Diphenyl-1,2-dihydrocyclopenta[f,g]acenaphthylene (3m) Orange solid; yield: 66 mg (40%); mp 219–221 °C. 1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 6.9 Hz, 2 H), 7.51–7.53 (m, 4 H), 7.46 (d, J = 7.0 Hz, 2 H), 7.34–7.38 (m, 4 H), 7.30 (m, 2 H), 3.55 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 146.9, 137.6, 136.3, 135.7, 135.4, 130.0, 128.4, 126.8, 126.0, 120.8, 32.6. HRMS (EI): m/z calcd for C26H18: 330.1409; found: 330.1399. 5,6-Bis(2-chlorophenyl)-1,2-dihydrocyclopenta-[f,g]acenaphthylene (3n) Yellow solid; yield: 46 mg (23%); mp 207–210 °C. 1H NMR (400 MHz, CDCl3): δ = 7.69 (dd, J = 15.4, 6.9 Hz, 2 H), 7.41–7.45 (m, 4 H), 7.30 (d, J = 6.0 Hz, 1 H), 7.11–7.29 (m, 5 H), 3.52 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 147.3, 147.3, 138.2, 137.6, 135.4, 135.1, 134.0, 133.9, 132.3, 132.2, 130.2, 129.5, 128.7, 128.5, 126.8, 126.6, 126.6, 126.2, 120.7, 120.6, 32.7. HRMS (EI): m/z calcd for C26H16Cl2: 398.0629; found: 398.0616. 5-Butyl-6-phenyl-1,2-dihydrocyclopenta-[f,g]acenaphthylene (3o) Yellow solid; yield: 103 mg (66%); mp 87–88 °C. 1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 6.9 Hz, 1 H), 7.58–7.62 (m, 3 H), 7.47–7.50 (m, 2 H), 7.34–7.41 (m, 3 H), 3.48 (s, 4 H), 2.94 (t, J = 6.5 Hz, 2 H), 1.80 (t, J = 6.4 Hz, 2 H), 1.41–1.50 (m, 2 H), 0.92 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 146.3, 145.7, 139.7, 137.4, 136.7, 136.5, 136.3, 135.1, 129.5, 128.4, 127.0, 126.7, 124.6, 124.6, 120.5, 120.5, 33.6, 32.6, 32.4, 27.0, 23.0, 14.0. HRMS (EI): m/z calcd for C24H22: 310.1722; found: 310.1718. 5-Phenyl-6-propyl-1,2-dihydrocyclopenta[f,g]-acenaphthylene (3p) Yellow solid; yield: 96 mg (65%); mp 105–106 °C. 1H NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 6.9 Hz, 1 H), 7.58–7.62 (m, 3 H), 7.48 (t, J = 7.6 Hz, 2 H), 7.34–7.40 (m, 3 H), 3.48 (s, 4 H), 2.92 (t, J = 6.5 Hz, 2 H), 1.82–1.87 (m, 2 H), 1.01 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 146.3, 145.7, 139.5, 137.6, 136.7, 136.5, 136.3, 135.1, 129.5, 128.4, 126.9, 126.7, 124.6, 124.6, 120.6, 120.5, 32.6, 32.4, 29.4, 24.7, 14.5. HRMS (EI): m/z calcd for C23H20: 296.1565; found: 296.1568.
  • 16 Dibenzo[j,l]fluoranthene (4) A mixture of Cs2CO3 (391 mg, 1.2 mmol), PdCl2(PCy3)2 (59 mg, 0.08 mmol), 1,2-bis(2-chlorophenyl)acenaphthylene (3d; 149.2 mg, 0.4 mmol), and NMP (4 mL) in a thick-walled Pyrex tube was purged with N2 for 5 min. The tube sealed, heated at the reflux for 24 h, and cooled to r.t. The suspension was diluted with CH2Cl2 (10 mL) and filtered through a 3-cm-thick layer of Celite. The filtrate was concentrated under reduced pressure, and the residue was purified by chromatography [silica gel, PE–EtOAc (20:1)] to give yellow needle crystals; yield: 58 mg (48%). 1H NMR (400 MHz, CDCl3): δ = 8.93 (d, J = 7.5 Hz, 2 H), 8.82 (d, J = 7.9 Hz, 2 H), 8.58 (d, J = 7.1 Hz, 2 H), 7.91 (d, J = 8.2 Hz, 2 H), 7.81–7.67 (m, 6 H). 13C NMR (101 MHz, CDCl3): δ = 137.9, 133.8, 132.0, 130.9, 129.9, 129.4, 128.0, 127.6, 127.2, 126.2, 125.0, 123.7.