Boron trifluoride etherate → HCID 131728729, compound

HRID 600144Notes

Reaction equation

HRID 600144 reaction equation
[C:1]([C:4]([C@@:6]([C:21](=[O:23])[CH3:22])([C@:8]([C:18](=[O:20])[CH3:19])([C@:10]([C:15](=[O:17])[CH3:16])([C@@H:12]([CH3:14])[OH:13])[OH:11])[OH:9])[OH:7])=[O:5])(=[O:3])[CH3:2].[CH3:24][O:25][C:26]1[CH:31]=[CH:30][C:29](O)=[CH:28][CH:27]=1.B(F)(F)F.CCOCC>ClCCl>[CH3:24][O:25][C:26]1[CH:31]=[CH:30][C:29]([C@:15]2([CH3:16])[O:17][C@:4]([C:1](=[O:3])[CH3:2])([OH:5])[C@:6]([C:21](=[O:23])[CH3:22])([OH:7])[C@@:8]([C:18](=[O:20])[CH3:19])([OH:9])[C@@:10]2([C:12](=[O:13])[CH3:14])[OH:11])=[CH:28][CH:27]=1

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 90154-MethoxyphenolHCID 86631770HCID 86631770, compound

Product 1

HCID 131728729HCID 131728729, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

D-Fucose (3) (4.95 g, 30.14 mmol) was dissolved in 30 mL of acetic anhydride and 30 mL of pyridine and stirred for 12 h. The solvent was removed in vacuo. Column chromatography (2:1 hexane/EtOAc) yielded 10.15 g (quant.) of 1,2,3,4-tetraacetyl-D-fucose (as a mixture of α-and β-anomer). 1,2,3,4-tetraacetyl-D-fucose (20.0 g, 60.2 mmol) and p-methoxyphenol (MPOH) (10.46 g, 84.3 mmol) were dissolved in 220 mL of dichloromethane and cooled to 0° C. BF3.OEt2 (21.4 g, 19.0 mL, 150.5 mmol) was added and the mixture stirred overnight. The reaction mixture was quenched by addition of saturated NaHCO3 solution, washed 2 times with water, dried over Na2SO4, concentrated and the residue was purified by column chromatography (3:1 hexane/EtOAc) yielding 16.8 g (71%) of 4-methoxyphenyl 1,2,3,4tetraacetyl-α-D-fucose (Only the β-anomer reacts, α-anomer could be recovered). 4-methoxyphenyl 1,2,3,4-tetraacetyl-α-D-fucose (3.90 g, 9.85 mmol) was dissolved in 150 mL of methanol and 6 mL of 0.5 M NaOMe solution were added. The mixture was stirred for 6 h. The solvent was removed in vacuo. Column chromatography (3:1 dichloromethane/methanol) afforded 2.63 g (99%) as a colorless solid: [α]D: +201.6 (c=0.32, CH3OH). 1H NMR (CD3OD, 300 MHz) δ 1.18 (d, J=6.6 Hz, 3H), 3.74 (s, 3H), 3.89 (m, 2H), 4.09 (quart., J=6.0 Hz, 1H), 5.31 (d, J=3.6 Hz, 1H), 6.82 (d, J=9.3 Hz, 2H), 7.04 (d, J=9.3 Hz, 2H). 13C NMR (CD3OD, 75 MHz) 16.3, 55.7, 67.9, 69.5, 71.2, 73.2, 100.0, 115.1, 119.0, 152.2, 156.0. MALDI-HRMS: m/z [M+Na]+ calcd 293.0996, obsd 293.0994.

Workup

  1. additionas a mixture of α-and β-anomer)
  2. customThe reaction mixture was quenched by addition of saturated NaHCO3 solution
  3. washwashed 2 times with water
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. customthe residue was purified by column chromatography (3:1 hexane/EtOAc)

Sources & evidence

ORD record
ord-d5d813cdd2de4adca3483c1e8e6ad351
Source dataset
uspto-grants-2011_03
Patent number
US07901687B2

Reaction notes

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