Compound Q1

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InChIKey DTKJJDUYLZGXOY-FEBSWUBLSA-N

Compound data: CIF

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

O-phenyl chlorothionoformate (448.8 mg, 2.60 mmol) was added to a stirring solution of quinine (324.4 mg, 1.00 mmol) in anhydrous dichloromethane (10 mL) at room temperature. The resulting reaction was allowed to stir for 2.5 hours before the reaction was diluted with dichloromethane and quenched with a saturated solution of sodium bicarbonate. The contents of the quenched reaction were then transferred to a separatory funnel. The biphasic mixture was separated and the organic layer washed with brine, dried with magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography 3:2 chloroform/ethyl acetate to provide 133.3 mg (33% yield) of S-thiocarbamate Q1 as a tan foam. Co-crystallization with benzene provided colorless crystals of suitable quality for x-ray diffraction analysis. M.p. 158-160 °C. ¹H NMR (CDCl₃, 500 MHz): δ 8.81 (d, J = 4.6 Hz, 1H), 8.16 (d, J = 9.2 Hz, 1H), 7.64 (d, J = 4.7 Hz, 1H), 7.47 (dd, J = 9.3, 2.6 Hz, 1H), 7.25 (d, J = 3.1 Hz, 1H), 5.69 (ddd, J = 17.0, 10.1, 9.0 Hz, 1H), 5.21 (dd, J = 10.2, 1.4 Hz, 1H), 5.18 - 5.10 (m, 2H), 4.05 - 3.96 (m, 2H), 3.98 (s, 3H), 3.53 (dd, J = 11.2, 3.4 Hz, 1H), 3.42 (dd, J = 11.2, 4.8 Hz, 1H), 2.97 (ddd, J = 13.3, 13.3, 3.4 Hz, 1H), 2.61 (ddd, J = 14.3, 9.1, 4.1 Hz, 1H), 2.20 - 2.13 (m, 1H), 2.07 - 2.00 (m, 1H), 1.88 (ddd, J = 13.8, 11.8, 4.7 Hz, 1H), 1.85 - 1.79 (m, 1H), 1.68 (dddd, J = 13.9, 13.9, 4.9, 4.9 Hz, 1H). ¹³C NMR (CDCl₃, 125 MHz): δ 170.4, 158.7, 147.8, 144.8, 141.8, 137.5, 132.4, 127.8, 122.4, 119.6, 118.6, 100.7, 60.4, 55.9, 47.7, 47.6, 44.0, 39.2, 32.7, 32.0, 26.0. ¹H NMR (d₆-benzene, 500 MHz): δ 8.71 (d, J = 4.5 Hz, 1H), 8.25 (d, J = 9.2 Hz, 1H), 7.25 (d, J = 4.5 Hz, 1H), 7.21 (dd, J = 9.2, 2.7 Hz, 1H), 7.08 (d, J = 2.7 Hz, 1H), 5.33 (ddd, J = 17.1, 10.2, 9.1 Hz, 1H), 4.89 (dd, J = 10.2, 1.7 Hz, 1H), 4.70 (dd, 17.1, 1.0 Hz, 1H), 4.66 (d, J = 7.2 Hz, 1H), 3.89 (ddd, J = 13.6, 5.1, 2.6 Hz, 1H), 3.45 (s, 3H), 3.37 (dd, J = 14.4, 5.1 Hz, 1H), 2.97 (dd, J = 11.2, 3.1 Hz, 1H), 2.90 (dd, J = 11.2, 4.8 Hz, 1H), 2.44 (td, J = 13.2, 3.5 Hz, 1H), 1.83 (ddd, J = 9.6, 9.0, 4.6 Hz, 1H), 1.59 - 1.48 (m, 2H), 1.29 - 1.08 (m, 3H). ¹³C NMR (d₆-benzene, 125 MHz): δ 169.6, 158.8, 148.2, 145.8, 141.5, 137.9, 133.3, 128.4, 121.8, 119.4, 117.9, 101.4, 59.6, 55.3, 47.5, 47.4, 43.2, 39.1, 32.1, 31.9, 25.7. HRMS(ESI): m/z calc. for C₂₁H₂₄ClN₂O₂S [M+H]⁺: 403.1247, found: 403.1244.