Ethyl Acetate → (2S,4R)-N-t-butoxycarbonyl-4-t-butyldimethylsiloxy-2-[alpha-hydroxy-3-(tetrahydropyranyloxymethyl)benzyl]pyrrolidine

HRID 725953

Reaktionsgleichung

Reaktionsgleichung von HRID 725953
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[CH:10]=[C:11](Br)[CH:12]=[CH:13][CH:14]=1.[C:16]([O:20][C:21]([N:23]1[CH2:29][C@H:28]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:27][C@H:24]1[CH:25]=[O:26])=[O:22])([CH3:19])([CH3:18])[CH3:17].[Cl-].[NH4+].C(OCC)(=O)C>O1CCCC1.O>[C:16]([O:20][C:21]([N:23]1[CH2:29][C@H:28]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:27][C@H:24]1[CH:25]([OH:26])[C:11]1[CH:12]=[CH:13][CH:14]=[C:9]([CH2:8][O:7][CH:2]2[CH2:3][CH2:4][CH2:5][CH2:6][O:1]2)[CH:10]=1)=[O:22])([CH3:19])([CH3:18])[CH3:17]

Komponenten

7

Edukt 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 10969557tert-Butyl (2S,4R)-4-((tert-butyldimethylsilyl)oxy)-2-formylpyrrolidine-1-carboxylateHCID 152820642-[(3-Bromophenyl)methoxy]oxane

Produkt 1

HCID 22881079(2S,4R)-N-t-butoxycarbonyl-4-t-butyldimethylsiloxy-2-[alpha-hydroxy-3-(tetrahydropyranyloxymethyl)benzyl]pyrrolidineAusbeute 55,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A solution of 3-(tetrahydropyranyloxymethyl)bromobenzene (11.8 g, 43.5 mmol) in tetrahydrofuran (20 ml) was added dropwise to a solution of 1.6M n-butyl lithium-hexane solution (30 ml, 48 mmol) in tetrahydrofuran (100 ml) at -78° C. in a nitrogen stream over 15 minutes. This reaction solution was stirred at -78° C. for 40 minutes and then a solution of (2S,4R)-N-t-butoxycarbonyl-4-(t-butyldimethylsiloxy)prolinal (7.2 g, 21.9 mmol) in tetrahydrofuran (20 ml) was added dropwise over 20 minutes. The reaction solution was stirred at -78° C. for 30 minutes and then allowed to gradually warm and saturated aqueous ammonium chloride was added thereto. This solution was poured into a liquid mixture of ethyl acetate with water and the organic layer was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated in vacuo. The resulting oily residue was subjected to silica gel column chromatography (Wakogel™ C-300, heptane-ethyl acetate=6:1) to give (2S,4R)-N-t-butoxycarbonyl-4-t-butyldimethylsiloxy-2-[α-hydroxy-3-(tetrahydropyranyloxymethyl)benzyl]pyrrolidine (6.3 g, yield: 55.0%) as a yellow oily substance.

Aufarbeitung

  1. stirringThe reaction solution was stirred at -78° C. for 30 minutes
  2. temperatureto gradually warm
  3. washthe organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-e0ba0091955a41b9a9522f8562e011bf
Quelldatensatz
uspto-grants-1998_01
Patentnummer
US05707987

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