Reaktionsgleichung
COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:10])=CC=1.[F:23][C:24]1[C:29]([F:30])=[CH:28][CH:27]=[CH:26][C:25]=1[C@H:31]1[CH2:37][NH:36][C:35](=O)[C@H:34]([NH:39][C:40](=[O:46])[O:41][C:42]([CH3:45])([CH3:44])[CH3:43])[CH2:33][CH2:32]1>C1(C)C=CC=CC=1>[F:23][C:24]1[C:29]([F:30])=[CH:28][CH:27]=[CH:26][C:25]=1[C@H:31]1[CH2:37][NH:36][C:35](=[S:10])[C@H:34]([NH:39][C:40](=[O:46])[O:41][C:42]([CH3:45])([CH3:44])[CH3:43])[CH2:33][CH2:32]1Komponenten
Reaktionsbedingungen
- Temperatur
- 90 °C
Versuchsvorschrift
Lawesson's reagent [2,4-Bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide] (2.90 g, 7.18 mmol) was added to a suspension of tert-butyl (3R,6S)-6-(2,3-difluorophenyl)-2-oxoazepan-3-ylcarbamate (4.79 g, 14.1 mmol) in toluene (250 mL) and the mixture was heated to 90° C. After 1 h, the reaction was allowed to cool to ambient temperature and concentrated. Purification by silica gel chromatography (100% dichloromethane→85% dichloromethane/ethyl acetate) gave a white solid. This solid was repurified by silica gel chromatography (20% ethyl acetate/hexanes→30% ethyl acetate/hexanes) to give the title compound (4.81 g). MS 357.0 (M+1). 1H NMR (500 MHz, CDCl3) δ 8.30 (s, 1H), 7.10-7.04 (m, 2H), 6.94-6.91 (m, 1H), 6.50 (d, J=6.1 Hz, 1H), 4.62 (dd, J=10.3, 3.7 Hz, 1H), 4.13-3.88 (m, 1H), 3.36 (dd, J=14.7, 7.1 Hz, 1H), 3.07 (t, J=11.2 Hz, 1H), 2.32-2.21 (m, 2H), 2.14-2.12 (m, 1H), 1.79-1.72 (m, 1H), 1.47 (s, 9H).
Aufarbeitung
- temperatureto cool to ambient temperature
- concentrationconcentrated
- customPurification by silica gel chromatography (100% dichloromethane→85% dichloromethane/ethyl acetate)
- customgave a white solid
- customThis solid was repurified by silica gel chromatography (20% ethyl acetate/hexanes→30% ethyl acetate/hexanes)
Quellen und Nachweise
- ORD-Eintrag
- ord-a57e8dd6b9f249d4bd725013f7322427
- Quelldatensatz
- uspto-grants-2010_06
- Patentnummer
- US07732438B2
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