Benzenesulfonic Acid → 1-[(2R,3R,4R,5R)-3,4-bis{[tert-Butyl(dimethyl)silyl]oxy}-5-(hydroxymethyl)tetrahydro-2-furanyl]-3-(4-methoxybenzyl)-2,4(1H,3H)-pyrimidinedione

HRID 25676

반응식

HRID 25676 반응식
[H-].[Na+].COC1C=CC(C(C2C=CC(OC)=CC=2)[O:12][CH:13](C2C=CC=CC=2)[CH:14]2[O:18][CH:17]([N:19]3[CH:24]=[CH:23][C:22](=[O:25])[NH:21][C:20]3=[O:26])[CH:16]([O:27][Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[CH:15]2[O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])=CC=1.[CH3:57][O:58][C:59]1[CH:66]=[CH:65][C:62]([CH2:63]Cl)=[CH:61][CH:60]=1.C1(S(O)(=O)=O)C=CC=CC=1>CN(C)C=O.C(OCC)(=O)C>[Si:28]([O:27][C@@H:16]1[C@H:15]([O:35][Si:36]([C:39]([CH3:41])([CH3:42])[CH3:40])([CH3:37])[CH3:38])[C@@H:14]([CH2:13][OH:12])[O:18][C@H:17]1[N:19]1[CH:24]=[CH:23][C:22](=[O:25])[N:21]([CH2:63][C:62]2[CH:65]=[CH:66][C:59]([O:58][CH3:57])=[CH:60][CH:61]=2)[C:20]1=[O:26])([C:31]([CH3:33])([CH3:34])[CH3:32])([CH3:30])[CH3:29]

참가 물질

7

반응물 4

HCID 7371Benzenesulfonic AcidHCID 24758Sodium hydrideHCID 699934-Methyloxybenzyl chlorideHCID 1317247641-[5-[Bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-3,4-bis-(tert-butyl-dimethyl-silanyloxy)-tetrahydro-furan-2-yl]-1H-pyrimidine-2,4-dione

생성물 1

HCID 151026051-[(2R,3R,4R,5R)-3,4-bis{[tert-Butyl(dimethyl)silyl]oxy}-5-(hydroxymethyl)tetrahydro-2-furanyl]-3-(4-methoxybenzyl)-2,4(1H,3H)-pyrimidinedione수율 59%

시약·촉매·용매 2

HCID 6228Dimethylformamide용매2회HCID 8857Ethyl Acetate용매2회

반응 조건

온도
0 °C

실험 절차

Following the procedure (Myers, A. G.; Gin, D. Y.; Rogers, D. H., J. Amer. Chem. Soc., 1994, 116, 4697-4718), a suspension of sodium hydride (1.55 g, 38.75 mmole, 60% oil dispersion) in anhydrous dimethylformamide (40 ml) was cooled at 0° C. under argon, and to this mixture was added a solution of 1-[5-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-3,4-bis-(tert-butyl-dimethyl-silanyloxy)-tetrahydro-furan-2-yl]-1H-pyrimidine-2,4-dione (20 g, 25.8 mmole, obtained from Reference Example 1) in anhydrous dimethylformamide (35 ml) over a period of 15 min. Neat p-methoxybenzyl chloride (7 ml, 51 mmole) was added to this solution. The resulting mixture was stirred at 0° C. for 15 h under argon, and diluted with ethyl acetate (700 ml). The organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated to dryness in vacuo. The oily residue was dissolved in chloroform (200 ml) and cooled at 0° C. under nitrogen. Benzenesulfonic acid (6 g, 37.93 mmole) was added portionwise, and the resulting red solution was stirred at 0° C. under nitrogen for 2 h. The mixture was diluted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated to dryness in vacuo. The residue was chromatographed (flash column, silica gel, methylene chloride:diethyl ether:methanol=95:3:2) to give 1-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(hydroxymethyl)tetrahydro-2-furanyl]-3-(4-methoxybenzyl)-2,4(1H,3H)-pyrimidinedione as white solid (9 g, 59%).

후처리

  1. washThe organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution
  2. dry with materialdried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated to dryness in vacuo
  5. dissolutionThe oily residue was dissolved in chloroform (200 ml)
  6. temperaturecooled at 0° C. under nitrogen
  7. stirringthe resulting red solution was stirred at 0° C. under nitrogen for 2 h
  8. washThe organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated to dryness in vacuo
  12. customThe residue was chromatographed (flash column, silica gel, methylene chloride:diethyl ether:methanol=95:3:2)

출처 및 근거

ORD 기록
ord-59f28981d8944a63b3f8938c9a99b206
출처 데이터셋
uspto-grants-2005_02
특허 번호
US06858591B2

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