Dichloromethane → tert-butyl (8S,9aR)-8-hydroxy-5-oxohexahydro-1H-pyrrolo[1,2-a][1,4]diazepine-2(3H)-carboxylate

HRID 1050308Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1050308
[N+](C1C=CC(C([O:10][C@@H:11]2[CH2:28][N:14]3[C:15](=[O:27])[CH2:16][CH2:17][N:18]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:19][C@H:13]3[CH2:12]2)=O)=CC=1)([O-])=O.C(=O)([O-])[O-].[K+].[K+].ClCCl>CO>[OH:10][C@@H:11]1[CH2:28][N:14]2[C:15](=[O:27])[CH2:16][CH2:17][N:18]([C:20]([O:22][C:23]([CH3:24])([CH3:25])[CH3:26])=[O:21])[CH2:19][C@H:13]2[CH2:12]1

Komponenten

5

Edukt 3

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 86723191tert-butyl (8S,9aR)-8-[(4-nitrobenzoyl)oxy]-5-oxohexahydro-1H-pyrrolo[1,2-a][1,4]diazepine-2(3H)-carboxylate

Produkt 1

HCID 86723192tert-butyl (8S,9aR)-8-hydroxy-5-oxohexahydro-1H-pyrrolo[1,2-a][1,4]diazepine-2(3H)-carboxylateAusbeute 64,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

tert-Butyl (8S,9aR)-8-[(4-nitrobenzoyl)oxy]-5-oxohexahydro-1H-pyrrolo[1,2-a][1,4]diazepine-2(3H)-carboxylate (156 mg, 0.372 mmol, 1.0 equivalent, Part E) was dissolved in methanol (3 mL). Potassium carbonate (20 mg, 0.145 mmol, 0.39 equivalent) was added and stirring was continued at room temperature for 30 minutes. The solvent was removed in vacuo, and the crude material was loaded onto a 12-g silica column with dichloromethane and eluted with 0-5% methanol:dichloromethane over 15 minutes, held at 5% methanol:dichloromethane for five minutes, then eluted with 10% methanol:dichloromethane for 10 minutes to afford the titled compound (65 mg, 0.240 mmol, 64.6% yield over two steps) as a white solid. 1H NMR (300 MHz, CDCl3) δ ppm 4.44 (t, J=3.7 Hz, 1H), 4.39-3.86 (m, J=79.8 Hz, 2H), 4.06 (dt, J=17.5, 8.9 Hz, 1H), 3.83 (dd, J=13.2, 2.3 Hz, 1H), 3.51 (dd, J=13.2, 3.7 Hz, 1H), 3.35-2.96 (br s, 1H), 2.74-2.46 (m, 3H), 2.24 (dd, J=13.2, 6.0 Hz, 1H), 1.74 (ddd, J=12.0, 9.0, 3.0 Hz, 1H), 1.48 (s, 9H); MS (ESI+) m/z 270.9 (M+H)+.

Aufarbeitung

  1. customThe solvent was removed in vacuo
  2. washeluted with 0-5% methanol
  3. waitdichloromethane over 15 minutes
  4. waitdichloromethane for five minutes
  5. washeluted with 10% methanol

Quellen und Nachweise

ORD-Eintrag
ord-5fe8ef599931408890150dfc56938306
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09382258B2

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