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

HRID 68391

반응식

HRID 68391 반응식
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

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 24437Sodium Sulfite용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-92ea649787e74abf95600df59ccc4d3c
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08822456B2

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