Triethylamine → (3S,3aR,5R)-5-[(benzyloxy)methyl]-3-methyl-3,3a,4,5-tetrahydro-7H-pyrano[3,4-c][1,2]oxazole

HRID 590606노트

반응식

HRID 590606 반응식
Cl[O-].[Na+].[CH2:4]([O:11][CH2:12][C@H:13]([O:18][CH2:19][CH:20]=[N:21][OH:22])[CH2:14][CH:15]=[CH:16][CH3:17])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C(N(CC)CC)C>ClCCl>[CH2:4]([O:11][CH2:12][C@@H:13]1[O:18][CH2:19][C:20]2=[N:21][O:22][C@@H:16]([CH3:17])[C@@H:15]2[CH2:14]1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

참가 물질

5

반응물 3

HCID 8471TriethylamineHCID 23665760Sodium HypochloriteHCID 867010832-{[(2R)-1-(benzyloxy)hex-4-en-2-yl]oxy}-N-hydroxyethanimine

생성물 1

HCID 86701084(3S,3aR,5R)-5-[(benzyloxy)methyl]-3-methyl-3,3a,4,5-tetrahydro-7H-pyrano[3,4-c][1,2]oxazole

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
25 °C

실험 절차

An aqueous solution of sodium hypochlorite (6.15% solution, 6.6 L) was slowly added to a solution of 2-{[(2R)-1-(benzyloxy)hex-4-en-2-yl]oxy}-N-hydroxyethanimine (C15) (660 g, 2.51 mol) and triethylamine (19 g, 0.19 mol) in dichloromethane (6.6 L) at 25° C. After completion of the addition, the reaction mixture was stirred at 25° C. for 30 minutes. The organic layer was washed with water (3×3 L), dried over sodium sulfate, filtered, and concentrated in vacuo. Purification via chromatography on silica gel (Eluent: ethyl acetate in petroleum ether) provided (3S,3aR,5R)-5-[(benzyloxy)methyl]-3-methyl-3,3a,4,5-tetrahydro-7H-pyrano[3,4-c][1,2]oxazole (C16) as a white solid. Yield: 90 g, 0.34 mol, 14%. The indicated relative stereochemistry of compound C16 was assigned based on nuclear Overhauser enhancement studies, which revealed interactions of the methine proton on carbon 3a with both the protons of the methyl group on carbon 3 and the methine proton on carbon 5. LCMS m/z 261.9 [M+H+]. 1H NMR (400 MHz, CDCl3) δ 7.24-7.39 (m, 5H), 4.69 (d, J=13.7 Hz, 1H), 4.57 (AB quartet, JAB=12.2 Hz, ΔνAB=13.8 Hz, 2H), 4.13-4.25 (m, 2H), 3.62-3.70 (m, 1H), 3.55 (dd, half of ABX pattern, J=10, 6 Hz, 1H), 3.47 (dd, half of ABX pattern, J=10, 4 Hz, 1H), 2.93 (br ddd, J=11, 11, 7 Hz, 1H), 2.11 (br dd, J=12.6, 6.8 Hz, 1H), 1.45-1.56 (m, 1H), 1.45 (d, J=6.2 Hz, 3H).

후처리

  1. additionAfter completion of the addition
  2. washThe organic layer was washed with water (3×3 L)
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification via chromatography on silica gel (Eluent: ethyl acetate in petroleum ether)

출처 및 근거

ORD 기록
ord-decc22653db5413f998dcb572b4e89ca
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09233981B1

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