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Acetic Acid → (2S,6S)-6-((2R,3R)-3-(benzyloxymethoxy)-2-(tert-butyldimethylsilyloxy)butyl)-2-((E)-4-((2R,6S)-6-(((2R,6S)-6-((S)-4-hydroxy-2-(4-methoxybenzyloxyl)butyl)-4-methylene-tetrahydro-2H-pyran-2-yl)methyl)-4-methylene-tetrahydro-2H-pyran-2-yl)-2-methylbut-3-en-2-yl)-2-methoxy-dihydro-2H-pyran-3(4H)-one

HRID 509210
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HRID 509210 반응식
[CH2:1]([O:8][CH2:9][O:10][C@H:11]([CH3:83])[C@H:12]([O:75][Si:76]([C:79]([CH3:82])([CH3:81])[CH3:80])([CH3:78])[CH3:77])[CH2:13][C@H:14]1[O:19][C@:18]([C:22]([CH3:73])(/[CH:24]=[CH:25]/[C@H:26]2[CH2:31][C:30](=[CH2:32])[CH2:29][C@@H:28]([CH2:33][C@H:34]3[CH2:39][C:38](=[CH2:40])[CH2:37][C@@H:36]([CH2:41][C@@H:42]([O:63][CH2:64][C:65]4[CH:70]=[CH:69][C:68]([O:71][CH3:72])=[CH:67][CH:66]=4)[CH2:43][CH2:44][O:45][Si](C(C)(C)C)(C4C=CC=CC=4)C4C=CC=CC=4)[O:35]3)[O:27]2)[CH3:23])([O:20][CH3:21])[C:17](=[O:74])[CH2:16][CH2:15]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1COCC1.CC(O)=O>CN(C=O)C>[CH2:1]([O:8][CH2:9][O:10][C@H:11]([CH3:83])[C@H:12]([O:75][Si:76]([C:79]([CH3:82])([CH3:81])[CH3:80])([CH3:77])[CH3:78])[CH2:13][C@H:14]1[O:19][C@:18]([C:22]([CH3:73])(/[CH:24]=[CH:25]/[C@H:26]2[CH2:31][C:30](=[CH2:32])[CH2:29][C@@H:28]([CH2:33][C@H:34]3[CH2:39][C:38](=[CH2:40])[CH2:37][C@@H:36]([CH2:41][C@@H:42]([O:63][CH2:64][C:65]4[CH:70]=[CH:69][C:68]([O:71][CH3:72])=[CH:67][CH:66]=4)[CH2:43][CH2:44][OH:45])[O:35]3)[O:27]2)[CH3:23])([O:20][CH3:21])[C:17](=[O:74])[CH2:16][CH2:15]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

6

반응물 4

HCID 176Acetic AcidHCID 8028TetrahydrofuranHCID 2724141Tetrabutylammonium FluorideHCID 131733237(2S,6S)-6-((2R,3R)-3-(benzyloxymethoxy)-2-(tert-butyldimethylsilyloxy)butyl)-2-((E)-4-((2R,6S)-6-(((2R,6S)-6-((S)-4-(tert-butyldiphenylsilyloxy)-2-(4-methoxybenzyloxyl)butyl)-4-methylene-tetrahydro-2H-pyran-2-yl)methyl)-4-methylene-tetrahydro-2H-pyran-2-yl)-2-methylbut-3-en-2-yl)-2-methoxy-dihydro-2H-pyran-3(4H)-one

생성물 1

HCID 131733238
(2S,6S)-6-((2R,3R)-3-(benzyloxymethoxy)-2-(tert-butyldimethylsilyloxy)butyl)-2-((E)-4-((2R,6S)-6-(((2R,6S)-6-((S)-4-hydroxy-2-(4-methoxybenzyloxyl)butyl)-4-methylene-tetrahydro-2H-pyran-2-yl)methyl)-4-methylene-tetrahydro-2H-pyran-2-yl)-2-methylbut-3-en-2-yl)-2-methoxy-dihydro-2H-pyran-3(4H)-one
수율 90.2%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매3회

실험 절차

To stirring solution of TBDPS ether 7 (119 mg, 0.101 mmol, 1.0 equiv) in DMF, was added a solution containing 1.0 M TBAF in THF (101 μL, 0.101 mmol, 1.0 equiv), and 1.0 M AcOH in DMF (101 μL, 0.101 mmol, 1.0 equiv) in additional DMF (300 μL), via cannula, rinsing once with DMF (300 μL). Stirring continued at rt for 21 h, and the reaction mixture was diluted with 40% EtOAc/hexanes (5 mL) and quenched with water (5 mL). The phases were separated and the aqueous phase was extracted three times with 40% EtOAc/hexanes (5 mL). The combined organic phases were dried over Na2SO4, filtered, and concentrated under reduced pressure. Purification was accomplished using flash column chromatography with a 3×8 cm silica gel column, eluting with 30% EtOAc/hexanes, collecting 13×100 mm test tube fractions. The product containing fractions (6-35) were combined and concentrated under reduced pressure to provide pure alcohol 22 (85.2 mg, 90%) as a clear viscous oil: Rf=0.21 (30% EtOAc/hexanes); [α]D20=+3.1 (c=1.03, CHCl3); 500 MHz 1H NMR (CDCl3) δ 7.38-7.24 (m, 7H), 6.88 (d, J=8.3 Hz, 2H), 6.04 (d, J=16.1 Hz, 1H), 5.46 (dd, J=16.1 6.3, Hz, 1H), 4.80 (d, J=6.8 Hz, 1H), 4.78 (d, J=6.8 Hz, 1H), 4.73 (d, J=1.5 Hz, 2H), 4.67 (s, 1H), 4.63 (s, 2H), 4.59 (s, 1H), 4.50 (d, J=10.7 Hz, 1H), 4.46 (d, J=10.7 Hz, 1H), 4.13-4.09 (m, 1H), 4.07 (ddd, J=9.0, 4.1, 2.4 Hz, 1H), 3.91-3.86 (m, 1H), 3.84-3.70 (m, 4H), 3.80 (s, 3H), 3.56-3.42 (m, 3H), 3.29 (s, 3H), 2.44 (dd, J=8.3, 5.9, Hz, 2H), 2.35 (s, 1H), 2.28-2.17 (m, 4H), 2.04-1.89 (m, 8H), 1.80 (ddd, J=14.3, 8.4, 2.5 Hz, 1H), 1.75-1.56 (m, 4H), 1.52 (ddd, J=11.2, 9.3, 3.4 Hz, 1H), 1.14 (d, J=6.3 Hz, 3H), 1.12 (s, 3H), 1.09 (s, 3H), 0.88 (s, 9H), 0.08 (s, 3H), 0.08 (s, 3H); 125 MHz 13C NMR (CDCl3) δ 207.5, 159.5, 144.6, 144.4, 138.0, 137.3, 130.6, 129.7, 129.2, 128.6, 128.0, 127.9, 114.1, 109.0, 108.9, 104.0, 93.4, 79.4, 75.4 (×2), 75.2, 75.1, 75.0, 72.0, 70.8, 69.8, 69.6, 60.5, 55.5, 52.8, 44.4, 42.9, 41.8, 41.5, 41.2, 41.0 (×2), 40.5, 38.2, 37.7, 36.8, 30.7, 26.1, 23.1, 22.1, 18.3, 14.0, −3.8, −4.4; 125 MHz DEPT 13C NMR (CDCl3) CH3 δ 55.5, 52.8, 26.1, 23.1, 22.1, 14.0, −3.8, −4.4; CH2 δ 109.0, 108.9, 93.4, 72.0, 69.6, 60.5, 42.9, 41.8, 41.5, 41.2, 41.0 (×2), 40.5, 38.2, 37.7, 36.8, 30.6; CH δ 137.3, 129.7, 129.2, 128.6, 128.0, 127.9, 114.1, 79.4, 75.4 (×2), 75.2, 75.1, 75.0, 70.8, 69.8; CH0 δ 207.5, 159.5, 144.6, 144.4, 138.0, 130.6, 104.0, 44.4, 18.3; IR (neat) 3446, 2937, 2857, 2360, 1725, 1652, 1613, 1514, 1463, 1381, 1303, 1250, 1113, 1042, 777 cm−1; HRMS (EI+) calcd for C53H78O10Si (M-MeOH) 902.5370. found 902.5381.

후처리

  1. additionwas added a solution
  2. washvia cannula, rinsing once with DMF (300 μL)
  3. additionthe reaction mixture was diluted with 40% EtOAc/hexanes (5 mL)
  4. customquenched with water (5 mL)
  5. customThe phases were separated
  6. extractionthe aqueous phase was extracted three times with 40% EtOAc/hexanes (5 mL)
  7. dry with materialThe combined organic phases were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customPurification
  11. washeluting with 30% EtOAc/hexanes
  12. customcollecting 13×100 mm test tube fractions
  13. additionThe product containing fractions (6-35)
  14. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-8f6f22bd1d8d47b89bffc14cbb280f24
출처 데이터셋
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09096550B2

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