Niobium Pentachloride Catalyzed Multicomponent Povarov Reaction

Abstract

A single-step method for the synthesis of furan- and pyranoquinoline derivatives through multicomponent Povarov reactions between aniline derivatives, benzaldehyde and two different enol ethers (2,3-dihydrofuran and 3,4-dihydropyran) using niobium pentachloride as catalyst under mild conditions, providing good yields and high diastereoselectivity, is described.

Key words

niobium pentachloride - multicomponent Povarov reaction - furanoquinolines - pyranoquinolines - Lewis acid

• References

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• 12 General Procedure for the Multicomponent Povarov Reaction of Benzaldehyde, Aniline Derivatives and Enol Ether with NbCl₅ : To a solution of niobium pentachloride (10 mol% or 25 mol%) in anhyd MeCN (2.0 mL), maintained at r.t. under a nitrogen atmosphere, was added a solution of the benzaldehyde (1.0 mmol), 2,3-dihydrofuran or 3,4-dihydropyran (1.0 mmol) and the respective aniline (3a–g; 1.0 mmol) in anhyd MeCN (3.0 mL). After completion of the addition, stirring was continued at r.t. The reaction mixture was quenched with H₂O addition (3.0 mL). The mixture was extracted with EtOAc (10.0 mL). The organic layer was separated and washed with sat. NaHCO₃ solution (3 × 10.0 mL), sat. brine (2 × 10.0 mL), and then dried over anhyd MgSO₄. The solvent was removed under vacuum and the products were purified by column chromatography through silica gel using mainly a mixture of hexane and EtOAc (9.0:1.0) as eluent. (3aS,4S,9bS)-4-Phenyl-2,3,3a,4,5,9b-hexahydrofuran-[3,2-c]quinoline (7a): ¹H NMR (300 MHz, CDCl₃): δ = 7.47 (d, 1 H, J ₁ = 7.6 Hz), 7.40–7.43 (m, 5 H), 7.10 (dd, 1 H, J ₁ = 8.0 Hz, J ₂ = 7.0 Hz), 6.82 (dd, 1 H, J ₁ = 7.6 Hz, J ₂ = 7.0 Hz), 6.61 (d, 1 H, J = 8.0 Hz), 5.29 (d, 1 H, J = 7.9 Hz), 4.71 (d, 1 H, J = 2.4 Hz), 3.70–3.88 (m, 2 H), 2.80 (m, 1 H), 2.21 (m, 1 H), 1.55 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 143.9 (C), 141.2 (C), 129.1 (CH), 127.6 (2 × CH), 127.3 (CH), 126.6 (CH), 125.5 (2 × CH), 121.7 (C), 118.2 (CH), 113.9 (CH), 74.9 (CH), 65.8 (CH₂), 56.5 (CH), 44.8 (CH), 23.7 (CH₂). IR (film): 3348, 2975, 2855, 1615, 1480, 1039 cm^–1. MS: m/z = 251 [M]⁺, 220, 206, 174, 130, 115, 91, 77. (3aS,4R,9bS)-4-Phenyl-2,3,3a,4,5,9b-hexahydrofuran-[3,2-c]quinoline (8a): ¹H NMR (300 MHz, CDCl₃): δ = 7.37 (d, 1 H, J = 7.0 Hz), 7.27–7.35 (m, 5 H), 7.06 (dd, 1 H, J ₁ = 8.3 Hz, J ₂ = 7.0 Hz), 6.73 (dd, 1 H, J ₁ = 8.3 Hz, J ₂ = 7.7 Hz), 6.56 (d, 1 H, J = 7.7 Hz), 4.54 (d, 1 H, J = 4.9 Hz), 3.96 (m, 1 H), 3.77 (m, 1 H), 3.74 (d, 1 H, J = 11.2 Hz), 2.40 (m, 1 H), 1.95 (m, 1 H), 1.65 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 145.8 (C), 142.1 (C), 131.6 (CH), 129.6 (CH), 129.1 (CH), 128.7 (CH), 128.6 (CH), 120.5 (CH), 118.8 (C), 115.1 (CH), 76.63 (CH), 65.6 (CH₂), 58.2 (CH), 43.8 (CH), 29.3 (CH₂). IR (film): 3348, 2975, 2855, 1615, 1480, 1039 cm^–1. MS: m/z = 251 [M]⁺, 220, 206, 174, 130, 115, 91, 77. (4aS,5S,10bS)-5-Phenyl-3,4,4a,5,6,10b-hexahydro-2H-pyran[3,2-c]quinoline (9a): ¹H NMR (300 MHz, CDCl₃): δ = 7.35–7.44 (m, 5 H), 7.30 (m, 1 H), 7.09 (dt, 1 H, J ₁ = 7.7 Hz, J ₂ = 0.8 Hz), 6.79 (dt, 1 H, J ₁ = 7.7 Hz, J ₂ = 1.0 Hz), 6.60 (dd, 1 H, J ₁ = 7.7 Hz, J ₂ = 0.8 Hz), 5.33 (d, 1 H, J = 5.6 Hz), 4.69 (d, 1 H, J = 2.3 Hz), 3.85 (NH, 1 H), 3.58 (m, 1 H), 3.43 (dt, 1 H, J ₁ = 11.6 Hz, J ₂ = 2.5 Hz), 2.16 (m, 1 H), 1.47–1.58 (m, 2 H), 1.43 (m, 1 H), 1.31 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 145.6 (C), 141.5 (C), 129.2 (CH), 128.8 (CH), 128.7 (CH), 128.5 (CH), 128.0 (CH), 127.9 (CH), 127.2 (CH), 120.3 (C), 118.7 (CH), 114.8 (CH), 73.2 (CH), 61.0 (CH₂), 59.7 (CH), 39.3 (CH), 25.8 (CH₂), 18.4 (CH₂). IR (film): 3312, 2941, 2865, 1608, 1486, 1317, 1265, 1069, 737 cm^–1. MS: m/z = 265 [M]⁺, 234, 220, 194, 129, 117, 91, 77. (4aS,5R,10bS)-5-Phenyl-3,4,4a,5,6,10b-hexahydro-2H-pyran[3,2-c]quinoline (10a): ¹H NMR (300 MHz, CDCl₃): δ = 7.30–7.44 (m, 5 H), 7.22 (dd, 1 H, J ₁ = 7.7 Hz, J ₂ = 1.3 Hz), 7.09 (dt, 1 H, J ₁ = 7.7 Hz, J ₂ = 1.3 Hz), 6.71 (dt, 1 H, J ₁ = 7.3 Hz, J ₂ = 0.7 Hz), 6.53 (dd, 1 H, J ₁ = 7.7 Hz, J ₂ = 0.7 Hz), 4.72 (d, 1 H, J = 10.9 Hz), 4.39 (d, 1 H, J = 2.8 Hz), 4.10 (dt, 1 H, J ₁ = 11.4 Hz, J ₂ = 2.3 Hz), 3.72 (dt, 1 H, J ₁ = 11.4 Hz, J ₂ = 2.5 Hz), 2.11 (m, 1 H), 1.84 (tdt, 1 H, J ₁ = 13.4 Hz, J ₂ = 12.4 Hz, J ₃ = 4.5 Hz), 1.65 (tt, 1 H, J ₁ = 13.4 Hz, J ₂ = 4.5 Hz), 1.47 (m, 1 H), 1.33 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 145.1 (C), 142.7 (C), 131.3 (CH), 129.8 (CH), 129.0 (2 × CH), 128.3 (2 × CH), 128.2 (CH), 121.0 (C), 117.9 (CH), 114.5 (CH), 74.9 (CH), 69.0 (CH₂), 55.2 (CH), 39.3 (CH), 24.5 (CH₂), 22.4 (CH₂). IR (film): 3360, 2940, 2865, 1610, 1488, 1315, 1265, 1070, 737 cm^–1. MS: m/z = 265 [M]⁺, 234, 220, 194, 129, 117, 91, 77
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