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

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

• 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.