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Tin tetrachloride → (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate

HRID 1854238
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Reaktionsgleichung

Reaktionsgleichung von HRID 1854238
C(O[C@H:5]1[C@H:10]([NH:11][C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]2[C:31]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[C:25]3[C:20]2=[CH:21][CH:22]=[CH:23][CH:24]=3)=[O:16])=[S:13])[C@@H:9]([O:32][C:33](=[O:35])[CH3:34])[C@H:8]([O:36][C:37](=[O:39])[CH3:38])[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6]1)(=O)C.Cl[Sn](Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:37]([O:36][C@@H:8]1[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6][C@H:5]2[C@H:10]([N:11]=[C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]3[C:31]4[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=4[C:25]4[C:20]3=[CH:21][CH:22]=[CH:23][CH:24]=4)=[O:16])[S:13]2)[C@H:9]1[O:32][C:33](=[O:35])[CH3:34])(=[O:39])[CH3:38]
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Komponenten

5

Edukt 3

HCID 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 86638169(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

Produkt 1

HCID 86638170(3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetateAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

The thiourea from above (200 mg, 0.32 mmol) was dissolved in CH2Cl2 (4 mL) and SnCl4 (0.5 mL, 4.0 mmol) was added. Then the resulting mixture was stirred at room temperature for 16 h. The solution was diluted 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 (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate as a pale colourless foam (125 mg, 69% yield). 1H NMR 500 MHz, CDCl3) δ 1.88 (s, 3H), 2.04 (s, 3H), 2.12 (s, 3H), 3.69 (m, 1H), 3.81 (ddd, 1H, J=2.5, 5.5, 6.5 Hz), 4.12 (dd, 1H, J=2.5, 12.5 Hz), 4.21-4.26 (m, 2H), 4.55 (dd, 1H, J=6.0, 12.5 Hz), 4.72-4.75 (dd, 1H, J=6.5, 6.5 Hz), 4.95 (dd, 1H J=5.5, 9.5 Hz), 5.24 (dd, 1H J=6.5, 9.5 Hz), 6.01 (d, 1H, J=6.5 Hz), 7.35 (dd, 2H, J=7.1, 7.8 Hz), 7.44 (dd, 2H, J=7.0, 7.8 Hz), 7.59 (d, 2H, J=7.1 Hz), 7.81 (d, 2H, J=7.0 Hz). 13C NMR (125 MHz, CDCl3) δ 20.62, 20.71, 21.35, 46.78, 57.91, 63.70, 67.92, 69.46, 71.88, 72.52, 90.23, 120.71, 120.89, 123.83, 124.04, 125.15, 127.76, 127.97, 129.61, 129.72, 130.08, 141.31, 142.86, 152.11, 161.43, 169.11, 169.63, 170.23.

Aufarbeitung

  1. extractionthe resulting mixture was extracted with CH2Cl2 (3×10 mL)
  2. dry with materialthe combined organic extracts were dried (Na2SO4)
  3. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-e37196565d824955b5e1931d042514c4
Quelldatensatz
uspto-grants-2015_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08962664B2

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