Compound 37

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Compound data: 1H NMR

Compound data: 13C NMR

Compound data: COSY

Compound data: CIF

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

According to the general procedure C described for compound 26, trans-4-ethyl-1,2,3,4,4a,5,6,10b-octahydrobenzo[f]quinoline (43.1 mg, 0.20 mmol, 1.0 equiv.) was protonated with HBF₄^.OEt₂ (30.2 μL, 35.6 mg, 0.22 mmol, 1.1 equiv.), reacted with manganese (III) perchlorophthalocyanine chloride (23.1 mg, 0.020 mmol, 0.10 equiv.), AgSbF₆ (6.9 mg, 0.020 mmol, 0.10 equiv.), PhI=NTces (172.2 mg, 0.40 mmol, 2.0 equiv.), and 3Å molecular sieves (40 mg) in DCE (0.4 mL). After 2 h of reacting, another batch of PhI=NTces (86.1 mg, 0.20 mmol, 1.0 equiv.) was quickly added to the reaction mixture. The reaction was further stirred for 13 h. Following work-up, the crude material was purified by flash chromatography (50 mL basic Al₂O₃ Brockmann grade III, gradient elution 30% EtOAc/Hex (4 column volumes)→0%→1%→2%→3% MeOH/CH₂Cl₂ (2 column volumes each)), staining with KMnO₄ to afford the product as a white solid with green discoloration as a mixture of diastereomers. The relative configuration was determined by NOESY and crystallography data. Run 1 (53.6 mg, 0.121 mmol, 61% yield, 5:1 d.r.). Run 2 (53.8 mg, 0.122 mmol, 61% yield, 6:1 d.r.). Run 3 (49.3 mg, 0.112 mmol, 56% yield, 5:1 d.r.; 4.3 mg, 0.020 mmol, 10% rsm). Average overall yield: 59% (3% rsm) ± 2.9, 5:1 dr. Data for major diastereomer (±)37: ¹H NMR: (500 MHz, CDCl₃) δ 7.48 (dd, J = 7.6, 1.2 Hz, 1H), 7.35 (d, J = 7.7 Hz, 1H), 7.31 (td, J = 7.7, 1.5 Hz, 1H), 7.26 (td, J = 7.3, 1.1 Hz, 1H), 4.98 (dd, J = 4.2, 2.7 Hz, 1H), 4.74 (d, J = 10.9 Hz, 1H), 4.72 (d, J = 10.9 Hz, 1H), 3.05 (dt, J = 11.4, 3.0 Hz, 1H), 2.95 (dq, J = 14.4, 7.2 Hz, 1H), 2.75 (dt, J = 13.5, 2.3 Hz, 1H), 2.70 (dq J = 14.0, 6.7 Hz, 1H), 2.60-2.49 (m, 2H), 2.36-2.25 (m, 2H), 1.92-1.86 (m, 1H), 1.86-1.78 (m, 2H), 1.37 (qd, J = 12.7, 3.9 Hz, 1H), 1.08 (t, J = 7.2 Hz, 3H). ¹³C NMR: (101 MHz, CDCl₃) δ 139.92, 133.19, 129.69, 128.93, 127.08, 126.09, 93.72, 78.08, 57.90, 53.50, 52.36, 46.90, 42.47, 33.28, 29.18, 25.57, 9.64. HRMS: (ESI-TOF MS ES+) m/z calculated for C₁₇H₂₄Cl₃N₂O₃S [M+H]⁺: 441.0573, found 441.0567. Data for minor diastereomer (±)37: ¹H NMR: (500 MHz, CDCl₃) δ 7.61 (d, J = 6.9 Hz, 1H), 7.32 (t, J = 7.1 Hz, 1H), 7.28 (d, J = 6.7 Hz, 1H), 7.27-7.24 (m, 1H), 4.92 (dd, J = 11.2, 6.1 Hz, 1H), 4.74 (d, J = 10.8 Hz, 1H), 4.70 (d, J = 10.8 Hz, 1H), 3.01 (d, J = 11.5 Hz, 1H), 2.99-2.95 (m, 1H), 2.92 (dt, J = 14.3, 7.1 Hz, 1H), 2.68 (dq, J = 13.9, 7.3 Hz, 2H), 2.48 (dd, J = 12.6, 2.6 Hz, 1H), 2.30-2.19 (m, 2H), 1.89-1.76 (m, 2H), 1.63 (q, J = 11.7 Hz, 1H), 1.19 (qd, J = 12.7, 4.2 Hz, 1H), 1.03 (t, J = 7.1 Hz, 3H). HRMS: (ESI-TOF MS ES+) m/z calculated for C₁₇H₂₄Cl₃N₂O₃S [M+H]⁺: 441.0573, found 441.0566.