Sodium Chloride → tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamate

HRID 75756

Reaktionsgleichung

Reaktionsgleichung von HRID 75756
[CH2:1]([C@@H:8]1[C@@H:16]([OH:17])[C@H:15]([CH3:18])[O:14][C:13](=[O:19])[C@@H:12]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.FC(F)(F)S(O[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[Si](C)(C)C)(=O)=O.[F-].[Cs+].[Na+].[Cl-]>CC#N>[CH2:1]([C@@H:8]1[C@@H:16]([O:17][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C@H:15]([CH3:18])[O:14][C:13](=[O:19])[C@@H:12]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

6

Edukt 4

HCID 5234Sodium ChlorideHCID 25953Cesium fluorideHCID 33840072-(Trimethylsilyl)phenyl trifluoromethanesulfonateHCID 86701245tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate

Produkt 1

HCID 86701251tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamateAusbeute 11,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a solution of tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate (500 mg, 1.32 mmol, 1.00 equiv) in anhydrous CH3CN (13 mL) were added 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.480 mL, 1.98 mmol, 1.50 equiv) followed by CsF (500 mg, 3.29 mmol, 2.50 equiv). The resulting mixture was stirred at room temperature for 2 d. The reaction was then poured into ½ sat'd NaCl solution (20 mL), extracted with EtOAc (3×20 mL), and the combined organic extracts were dried over MgSO4, filtered, and concentrated to provide an oily yellow suspension. This was purified by automated silica gel column chromatograpy to provide tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamate (69 mg, 11%) as an amorphous light yellow solid: 1H NMR (400 MHz, CDCl3) δ 7.34-7.20 (m, 5H), 7.20-7.04 (m, 4H), 7.02-6.88 (d, J=8.7 Hz, 4H), 5.20-5.02 (dq, J=9.1, 6.4 Hz, 2H), 4.71-4.57 (m, 1H), 4.37-4.21 (t, J=8.9 Hz, 1H), 4.00-3.88 (dd, J=11.6, 7.3 Hz, 1H), 3.60-3.44 (s, 2H), 3.38-3.21 (m, 1H), 3.07-2.93 (dd, J=13.6, 3.1 Hz, 1H), 2.37-2.21 (t, J=12.5 Hz, 1H), 2.22-2.09 (m, 1H), 1.46-1.40 (s, 9H), 1.40-1.34 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 172.29, 159.20, 154.98, 139.50, 129.75, 129.11, 128.42, 126.19, 121.34, 115.48, 81.96, 80.19, 75.39, 72.88, 72.08, 52.98, 47.56, 35.29, 28.29, 18.98; ESIMS m/z 478.6 ([M+Na]+).

Aufarbeitung

  1. extractionextracted with EtOAc (3×20 mL)
  2. dry with materialthe combined organic extracts were dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customto provide an oily yellow suspension
  6. customThis was purified by automated silica gel column chromatograpy

Quellen und Nachweise

ORD-Eintrag
ord-f1d0d59e478143e0904373747c3052b7
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08835462B2

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