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Triethylamine → (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

HRID 2194649
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2194649
[C:1]([O:4][C@H:5]1[C@H:10]([NH2:11])[C@@H:9]([O:12][C:13](=[O:15])[CH3:14])[C@H:8]([O:16][C:17](=[O:19])[CH3:18])[C@@H:7]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:6]1)(=[O:3])[CH3:2].[CH:25]1[C:37]2[CH:36]([CH2:38][O:39][C:40]([N:42]=[C:43]=[S:44])=[O:41])[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[C:29]=2[CH:28]=[CH:27][CH:26]=1.C(N(CC)CC)C>N1C=CC=CC=1>[C:1]([O:4][C@H:5]1[C@H:10]([NH:11][C:43]([NH:42][C:40]([O:39][CH2:38][CH:36]2[C:35]3[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=3[C:29]3[C:37]2=[CH:25][CH:26]=[CH:27][CH:28]=3)=[O:41])=[S:44])[C@@H:9]([O:12][C:13](=[O:15])[CH3:14])[C@H:8]([O:16][C:17](=[O:19])[CH3:18])[C@@H:7]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:6]1)(=[O:3])[CH3:2]
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Komponenten

5

Edukt 3

HCID 8471TriethylamineHCID 202260[(2R,3S,4R,5R,6S)-3,4,6-triacetyloxy-5-aminooxan-2-yl]methyl acetateHCID 4154759Fmoc isothiocyanate

Produkt 1

HCID 86638169(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1049
Pyridine
Lösungsmittel

Versuchsvorschrift

The amine from above (220 mg) was dissolved in pyridine (5 mL) and 9-Fluorenylmethoxycarbonyl isothiocyanate (180 mg, 0.65 mmol) and triethylamine (0.02 mL) was added. Then the resulting mixture was stirred at room temperature for 16 h. The solution was concentrated and the residue taken up in CH2Cl2 (20 mL) and diluted with saturated aqueous NaHCO3 (20 mL), then the resulting mixture was extracted with CH2Cl2 (3×10 mL) and the combined organic extracts were dried (Na2SO4) and concentrated. Flash chromatography of the residue (EtOAc:hexanes 2:3) gave (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate as a white foam (360 mg, 89% yield over two steps). 1H NMR (600 MHz, CDCl3) δ 2.06 (s, 3H), 2.07 (s, 3H), 2.12 (s, 3H), 2.14 (s, 3H), 3.89 (ddd, 1H, J=2.4, 4.8, 9.6 Hz), 4.17 (dd, 1H, J=2.4, 12.5 Hz), 4.24 (dd, 1H, J=6.6, 6.6 Hz), 4.33 (dd, 1H, J=4.8, 12.5 Hz), 4.52 (s, 1H), 4.54 (s, 1H), 5.08-5.12 (m, 1H), 5.22 (dd, 1H, J=9.5, 9.6 Hz), 5.34 (dd, 1H, J=6.6, 9.5 Hz), 5.88 (d, 1H, J=6.6 Hz), 7.36 (dd, 2H, J=7.2, 7.8 Hz), 7.45 (dd, 2H, J=7.2, 7.8 Hz), 7.57 (d, 2H, J=7.8 Hz), 7.80 (d, 2H, J=7.2 Hz). 13C NMR (150 MHz, CDCl3) δ 20.62, 20.72, 20.77, 21.05, 46.49, 57.59, 61.65, 67.47, 68.40, 72.21, 72.87, 92.21, 120.09, 120.29, 124.84, 124.96, 125.32, 127.30, 127.83, 128.15, 128.25, 129.06, 141.37, 142.80, 152.16, 169.27, 169.34, 170.46, 170.72, 180.22.

Aufarbeitung

  1. concentrationThe solution was concentrated
  2. additiondiluted with saturated aqueous NaHCO3 (20 mL)
  3. extractionthe resulting mixture was extracted with CH2Cl2 (3×10 mL)
  4. dry with materialthe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-a47ec64919f9466fa653ee7a5559ada8
Quelldatensatz
uspto-grants-2012_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08334310B2

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