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

HRID 2035396ノート

反応式

HRID 2035396 の反応式
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

参加物

7

反応物 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、化合物

生成物 1

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-dd5c838f73c54a7bb9dba0eef31473bd
出典データセット
uspto-grants-2013_11
特許番号
US08575114B2

反応ノート

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