Methanesulfonic Acid → (3S,4S,5S)-2-(3-((tert-butyldiphenylsilyloxy)methyl)-4-chlorophenyl)-6-(hydroxymethyl)-2-methoxytetrahydro-2H-pyran-3,4,5-triol

HRID 2035396노트

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HRID 2035396 반응식
C[Si](C)(C)[O:3][C@H:4]1[C@@H:9]([O:10][Si](C)(C)C)[C@H:8]([O:15][Si](C)(C)C)[CH:7]([CH2:20][O:21][Si](C)(C)C)[O:6][C:5]1=[O:26].Br[C:30]1[CH:31]=[CH:32][C:33]([Cl:55])=[C:34]([CH:54]=1)[CH2:35][O:36][Si:37]([C:50]([CH3:53])([CH3:52])[CH3:51])([C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1.[Li][C:57](C)(C)C.CS(O)(=O)=O>O1CCCC1.CO>[Si:37]([O:36][CH2:35][C:34]1[CH:54]=[C:30]([C:5]2([O:26][CH3:57])[C@@H:4]([OH:3])[C@@H:9]([OH:10])[C@H:8]([OH:15])[CH:7]([CH2:20][OH:21])[O:6]2)[CH:31]=[CH:32][C:33]=1[Cl:55])([C:50]([CH3:53])([CH3:52])[CH3:51])([C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1

참가 물질

7

반응물 4

HCID 6395Methanesulfonic AcidHCID 57516661(5-Bromo-2-chlorobenzyloxy)(tert-butyl)diphenylsilaneHCID 67417628(3S,4S,5R)-3,4,5-tris(trimethylsilyloxy)-6-((trimethylsilyloxy)methyl)tetrahydro-2H-pyran-2-oneHCID 178418306HCID 178418306, 화합물

생성물 1

HCID 67419038(3S,4S,5S)-2-(3-((tert-butyldiphenylsilyloxy)methyl)-4-chlorophenyl)-6-(hydroxymethyl)-2-methoxytetrahydro-2H-pyran-3,4,5-triol수율 107.4%

시약·촉매·용매 2

HCID 887Methanol용매HCID 8028Tetrahydrofuran용매

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온도
-78 °C

실험 절차

To a solution of (3S,4S,5R)-3,4,5-tris(trimethylsilyloxy)-6-((trimethylsilyloxy)methyl)tetrahydro-2H-pyran-2-one (3.0 g, 6.5 mmol) and (5-bromo-2-chlorobenzyloxy)(tert-butyl)diphenylsilane (3.7 g, 7.8 mmol) in tetrahydrofuran (105 mL) at −78° C. under nitrogen was added t-BuLi (8.0 mL, 13.7 mmol) dropwise. Reaction was stirred at −78° C. for 5 hours and then a cold (−78° C.) solution of methanesulfonic acid (1.6 mL) in methanol (54 mL) was added to it via cannulation. The cold bath was then removed and the reaction mixture was stirred at room temperature overnight. The reaction solution was quenched with aqueous sodium bicarbonate and extracted with ethyl acetate (3×). The combined organic extract was washed with brine, dried over sodium sulfate and concentrated in vacuo to give (3S,4S,5S)-2-(3-((tert-butyldiphenylsilyloxy)methyl)-4-chlorophenyl)-6-(hydroxymethyl)-2-methoxytetrahydro-2H-pyran-3,4,5-triol (4.0 g, crude, mixture of 2 anomers at 2-position) as a white foam, which was used in the next step without purification.

후처리

  1. customReaction
  2. customThe cold bath was then removed
  3. stirringthe reaction mixture was stirred at room temperature overnight
  4. customThe reaction solution was quenched with aqueous sodium bicarbonate
  5. extractionextracted with ethyl acetate (3×)
  6. extractionThe combined organic extract
  7. washwas washed with brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-dd5c838f73c54a7bb9dba0eef31473bd
출처 데이터셋
uspto-grants-2013_11
특허 번호
US08575114B2

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