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Methanesulfonic Acid → (2S,3R,4S,5S,6R)-2-[4-chloro-3-[[4-(2,2-difluoroethoxy)phenyl]methyl]phenyl]-6-(hydroxymethyl)-2-methoxy-tetrahydropyran-3,4,5-triol

HRID 1913071
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1913071
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH:18]([F:20])[F:19])=[CH:12][CH:11]=2)[CH:3]=1.[Li][CH2:22]CCC.C[Si](C)(C)[O:28][C@@H:29]1[C@@H:34]([O:35][Si](C)(C)C)[C@H:33]([O:40][Si](C)(C)C)[C@@H:32]([CH2:45][O:46][Si](C)(C)C)[O:31][C:30]1=[O:51].CS(O)(=O)=O.C(=O)(O)[O-].[Na+]>CC(OC)(C)C.CCCCCC.CO>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C@@:30]2([O:51][CH3:22])[C@H:29]([OH:28])[C@@H:34]([OH:35])[C@H:33]([OH:40])[C@@H:32]([CH2:45][OH:46])[O:31]2)=[CH:3][C:4]=1[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH:18]([F:20])[F:19])=[CH:12][CH:11]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 5

HCID 6395Methanesulfonic AcidHCID 516892Sodium BicarbonateHCID 10994280(3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-onHCID 866851654-Bromo-1-chloro-2-[[4-(2,2-difluoroethoxy)phenyl]methyl]benzeneHCID 178418339Butyllithium

Produkt 1

HCID 86685166
(2S,3R,4S,5S,6R)-2-[4-chloro-3-[[4-(2,2-difluoroethoxy)phenyl]methyl]phenyl]-6-(hydroxymethyl)-2-methoxy-tetrahydropyran-3,4,5-triol
Ausbeute 14,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 8058HexaneLösungsmittel2×HCID 15413tert-Butyl methyl etherLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

Under Ar protection, 4-bromo-1-chloro-2-[[4-(2,2-difluoroethoxy)phenyl]methyl]benzene 12p (26.5 g, 73.3 mmol), MTBE (266 mL) and n-hexane (133 mL) were added into a 1 L reaction flask, stirred uniformly and cooled to −78° C., followed by dropwise addition of 2.4 M nBuLi (52 mL, 124.6 mmol) in 30 minutes. After stirring for 50 minutes at −78° C., a mixed solution of (3R,4S,5R,6R)-3,4,5-tris(trimethylsilyloxy)-6-(trimethylsilyloxymethyl)tetrahydropyran-2-one 2f (55 g, 117.3 mmol) in MTBE and n-hexane (60 mL:30 mL) was added within 20 minutes at −78° C. before the reaction mixture was stirred for 4 hours at −78° C. Thereafter, 130 mL methanol were added before stirring for 20 minutes. Then the reaction mixture was warmed to room temperature and stirred for 16 hours after methanesulfonic acid (25 g, 256.55 mmol) was added. 500 mL saturated sodium bicarbonate were added to the reaction mixture, stirred for 1 hour and partitioned. The aqueous phase was extracted with MTBE (100 mL×2) and the organic extract was combined, concentrated and purified by column chromatography (eluant: dichloromethane: methanol=100:1˜10:1) to obtain the title compound (2S,3R,4S,5S,6R)-2-[4-chloro-3-[[4-(2,2-difluoroethoxy)phenyl]methyl]phenyl]-6-(hydroxymethyl)-2-methoxy-tetrahydropyran-3,4,5-triol 12e (5 g, pale yellow solid), yield: 10%. MS m/z (ESI): 492.46 [M+18].

Aufarbeitung

  1. stirringAfter stirring for 50 minutes at −78° C.
  2. stirringwas stirred for 4 hours at −78° C
  3. stirringbefore stirring for 20 minutes
  4. temperatureThen the reaction mixture was warmed to room temperature
  5. additionwas added
  6. stirringstirred for 1 hour
  7. custompartitioned
  8. extractionThe aqueous phase was extracted with MTBE (100 mL×2)
  9. extractionthe organic extract
  10. concentrationconcentrated
  11. custompurified by column chromatography (eluant: dichloromethane: methanol=100:1˜10:1)

Quellen und Nachweise

ORD-Eintrag
ord-1bd2b032421746a0906d39d185c795ae
Quelldatensatz
uspto-grants-2013_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08609622B2

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