Pyridine → (3AR,5R)-5-((benzyloxy)methyl)-3a,4,5,7-tetrahydro-3H-pyrano[3,4-c]isoxazole

HRID 68391

Reaktionsgleichung

Reaktionsgleichung von HRID 68391
N1C=CC=CC=1.[CH2:7]([O:14][CH2:15][C@H:16]([O:20][CH2:21][CH:22]=[N:23][OH:24])[CH2:17][CH:18]=[CH2:19])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.ClN1C(=O)CCC1=O>ClCCl.S([O-])([O-])=O.[Na+].[Na+]>[CH2:7]([O:14][CH2:15][C@@H:16]1[O:20][CH2:21][C:22]2=[N:23][O:24][CH2:19][C@@H:18]2[CH2:17]1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Komponenten

6

Edukt 3

HCID 1049PyridineHCID 31398ChlorosuccinimideHCID 86640913((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oxime

Produkt 1

HCID 57475687(3AR,5R)-5-((benzyloxy)methyl)-3a,4,5,7-tetrahydro-3H-pyrano[3,4-c]isoxazole

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 24437Sodium SulfiteLösungsmittel

Versuchsvorschrift

Pyridine (23.1 mL, 286 mmol) was added to a solution of 2-{[(2R)-1-(benzyloxy)pent-4-en-2-yl]oxy}-N-hydroxyethanimine (C3) (35.6 g, 143 mmol) in dichloromethane (350 mL). N-Chlorosuccinimide (19.4 g, 145 mmol) was added in portions over roughly 2 hours. The reaction was stirred for 3 hours, then diluted with an aqueous solution of sodium sulfite (5 g in 100 mL water). The mixture was stirred for 20 minutes, and the aqueous layer was extracted with dichloromethane; the combined organic layers were washed with water, dried, and concentrated. Purification via silica gel chromatography (Eluent: 1:2 ethyl acetate/hexanes) afforded the product. Yield: 21.2 g, 85.7 mmol, 60%. 1H NMR (400 MHz, CDCl3) δ 7.28-7.40 (m, 5H), 4.77 (d, J=13.4 Hz, 1H), 4.55-4.65 (m, 3H), 4.22 (dd, J=13.5, 1.3 Hz, 1H), 3.79 (dd, J=11.7, 8.0 Hz, 1H), 3.69-3.76 (m, 1H), 3.57 (dd, half of ABX pattern, J=10.2, 5.9 Hz, 1H), 3.49 (dd, half of ABX pattern, J=10.2, 4.3 Hz, 1H), 3.40-3.5 (m, 1H), 2.21 (ddd, J=12.9, 6.5, 1.8 Hz, 1H), 1.57 (ddd, J=13, 12, 11 Hz, 1H).

Aufarbeitung

  1. stirringThe mixture was stirred for 20 minutes
  2. extractionthe aqueous layer was extracted with dichloromethane
  3. washthe combined organic layers were washed with water
  4. customdried
  5. concentrationconcentrated
  6. customPurification via silica gel chromatography (Eluent: 1:2 ethyl acetate/hexanes)
  7. customafforded the product

Quellen und Nachweise

ORD-Eintrag
ord-92ea649787e74abf95600df59ccc4d3c
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08822456B2

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