Trimethylsilyl triflate → 1-allyl-1-deoxy-2,3,4-tri-O-benzyl-alpha-L-fucopyranose

HRID 1721010Notes

Reaction equation

HRID 1721010 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:13]([CH3:32])[O:12]C1O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:33]([Si](C)(C)C)[CH:34]=[CH2:35].[CH3:40][Si](OS(C(F)(F)F)(=O)=O)(C)C>C(#N)C>[CH2:34]([C@@H:35]1[O:12][C@@H:13]([CH3:32])[C@@H:14]([O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C@@H:15]([O:16][CH2:17][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@@H:9]1[O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH:33]=[CH2:40]

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 69808AllyltrimethylsilaneHCID 2734155(3S,4R,5R,6S)-3,4,5-Tris(benzyloxy)-6-methyltetrahydro-2H-pyran-2-ol

Product 1

HCID 153448101-allyl-1-deoxy-2,3,4-tri-O-benzyl-alpha-L-fucopyranoseYield 79%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2,3,4-tri-O-benzyl-L-fucopyranose (11a, 10.0 g) in acetonitrile (100 ml) at 0° C., allyltrimethylsilane (12 ml) was added followed by trimethylsilyltrifluoromethanesulfonate (14.5 ml). The solution was warmed to room temperature and was stirred for 14 hours at room temperature. The mixture was quenched with water (100 ml) in an ice-water bath. The acetonitrile was evaporated in vacuo and the mixture was extracted with ethyl acetate (3×100 ml). The combined organic extracts were washed with saturated sodium carbonate solution, followed by saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The crude mixture was eluted on a silica gel column (150 ml, hexane:ethyl acetate, 10:1) to provide 1-allyl-1-deoxy-2,3,4-tri-O-benzyl-α-L-fucopyranose (11b, 9.2 g, 79%).

Workup

  1. customThe mixture was quenched with water (100 ml) in an ice-water bath
  2. customThe acetonitrile was evaporated in vacuo
  3. extractionthe mixture was extracted with ethyl acetate (3×100 ml)
  4. washThe combined organic extracts were washed with saturated sodium carbonate solution
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. washThe crude mixture was eluted on a silica gel column (150 ml, hexane:ethyl acetate, 10:1)

Sources & evidence

ORD record
ord-7977dd6953534378beaf585df6c9a2f8
Source dataset
uspto-grants-1996_04
Patent number
US05508387

Reaction notes

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