An Unprecedented Tandem Annulation of ω-Azido-1-alkynes with Diaryl­iodonium Salts: A Facile Synthesis of Polycyclic Quinolines

Abstract

Polysubstituted quinolines are synthesized through an unprecedented cascade annulation of ω-azido-1-alkynes with diaryliodonium salts, which serve as C2-building blocks. The reaction proceeds smoothly and is catalyzed by Cu(I) catalysts to give various quinolines in good isolated yields with simple operation under mild conditions.

Key words

quinolines - azides - alkynes - copper catalyst - tandem annulation

• References and Notes

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• 8 Preparation of 3aa; Typical Procedure: 6-Azido-1-phenyl-1-hexyne (2a; 0.3 mmol, 59.7 mg) was added to a solution of diphenyliodonium trifluoromethanesulfonate (1a; 0.6 mmol, 258 mg) and Cu₂O (0.045 mmol, 6.5 mg) in anhydrous DCE (2.0 mL) under a N₂ atmosphere. The reaction mixture was stirred at 60 °C for 24 h, and then poured into a mixture of sat. aq NaHCO₃ (5 mL) and CH₂Cl₂ (20 mL). The organic phase was separated, washed with sat. aq NaHCO₃ (2 × 5 mL), and then dried over anhydrous Na₂SO₄. Evaporation of the solvent followed by purification on silica gel provided 9-phenyl-2,3-dihydro-1H-cyclopenta[b]quinoline (3aa; 55 mg, 75% isolated yield) as a yellow solid. This product has been reported previously.⁵ 9-Phenyl-2,3-dihydro-1H-cyclopenta[b]quinoline (3aa): ¹H NMR (400 MHz, CDCl₃): δ = 8.07 (dd, J = 8.8, 1.0 Hz, 1 H), 7.66–7.58 (m, 2 H), 7.56–7.42 (m, 3 H), 7.42–7.32 (m, 3 H), 3.24 (t, J = 7.7 Hz, 2 H), 2.91 (t, J = 7.4 Hz, 2 H), 2.17 (quint, J = 7.5 Hz, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 167.68, 148.1, 142.8, 136.9, 133.8, 129.4 (2×CH), 129.0, 128.6 (2×CH), 128.4, 128.1, 126.3, 125.8, 125.6, 35.4, 30.5, 23.7. GC-MS: m/z calcd for C₁₈H₁₅N: 245; found: 245.
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• 11 Preparation of 5aa; Typical Procedure: 7-Azido-1-phenyl-1-heptyne (4a; 0.3 mmol, 63.9 mg) was added to a solution of diphenyliodonium trifluoromethanesulfonate (1a; 0.6 mmol, 258 mg) and Cu₂O (0.045 mmol, 6.5 mg) in anhydrous DCE (2.0 mL) under a N₂ atmosphere. The reaction mixture was stirred at 60 °C for 24 h, and then poured into a mixture of sat. aq NaHCO₃ (5 mL) and CH₂Cl₂ (20 mL). The organic phase was separated, washed with sat. aq NaHCO₃ (2 × 5 mL), and then dried over anhydrous Na₂SO₄. Evaporation of the solvent followed by purification on silica gel provided 9-phenyl-1,2,3,4-tetrahydroacridine (5aa; 52 mg, 67% isolated yield) as a yellow solid. This product has been reported⁵ previously. 9-Phenyl-1,2,3,4-tetrahydroacridine (5aa): ¹H NMR (400 MHz, CDCl₃): δ = 8.02 (d, J = 8.5 Hz, 1 H), 7.60 (ddd, J = 8.3, 5.1, 3.1 Hz, 1 H), 7.55–7.42 (m, 3 H), 7.35–7.27 (m, 2 H), 7.23 (dd, J = 8.0, 1.4 Hz, 2 H), 3.20 (t, J = 6.6 Hz, 2 H), 2.60 (t, J = 6.5 Hz, 2 H), 2.02–1.88 (m, 2 H), 1.84–1.70 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 159.2, 146.6, 146.4, 137.3, 129.2 (2×CH), 128.7 (2×CH), 128.5, 128.5, 127.8, 126.8, 125.9, 125.5, 34.4, 28.2, 23.2, 23.1. GC-MS: m/z calcd for C₁₉H₁₇N: 259; found: 259.
• 12 CCDC-1019165 (3da) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
• 13 Preparation of 7aa; Typical Procedure: 8-Azido-1-phenyl-1-octyne (6a; 0.3 mmol, 68.1 mg) was added to a solution of diphenyliodonium trifluoromethanesulfonate (1a; 0.6 mmol, 258 mg) and Cu₂O (0.045 mmol, 6.5 mg) in anhydrous DCE (2.0 mL) under a N₂ atmosphere. The reaction mixture was stirred at 60 °C for 24 h, and then poured into a mixture of sat. aq NaHCO₃ (5 mL) and CH₂Cl₂ (20 mL). The organic phase was separated, washed with sat. aq NaHCO₃ (2 × 5 mL), and then dried over anhydrous Na₂SO₄. Evaporation of the solvent followed by purification on silica gel provided 11-phenyl-7,8,9,10-tetrahydro-6H-cyclohepta[b]quinoline (7aa; 59 mg, 72% isolated yield) as a yellow solid. This product has been reported⁵ previously. 11-Phenyl-7,8,9,10-tetrahydro-6H-cyclohepta[b]quinoline (7aa): ¹H NMR (301 MHz, CDCl₃): δ = 8.03 (d, J = 8.3 Hz, 1 H), 7.60 (ddd, J = 8.3, 6.5, 1.8 Hz, 1 H), 7.55–7.42 (m, 3 H), 7.36–7.27 (m, 2 H), 7.26–7.19 (m, 2 H), 3.32–3.23 (m, 2 H), 2.73–2.66 (m, 2 H), 1.91–1.77 (m, 4 H), 1.67–1.53 (m, 2 H). ¹³C NMR (76 MHz, CDCl₃): δ = 165.0, 146.0, 145.6, 137.8, 134.0, 129.6 (2×CH), 128.8, 128.6 (2×CH), 128.3, 127.8, 127.1, 126.5, 125.7, 40.4, 32.1, 30.9, 28.7, 27.2. GC-MS: m/z calcd for C₂₀H₁₉N: 273; found: 273.

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