Boron trifluoride etherate → HCID 131736871, compound

HRID 1488278Notes

Reaction equation

HRID 1488278 reaction equation
[C:1]([O:4][CH:5]1[O:22][C@@H:21]([CH3:23])[C@@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@@H:6]1[O:7][C:8](=[O:10])[CH3:9])(=O)[CH3:2].OCC[NH:27][C:28](=[O:37])[O:29][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.B(F)(F)F.CCOCC.CCN(CC)CC>C(C#N)(C)=O>[C:8]([O:7][C@H:6]1[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@H:21]([CH3:23])[O:22][C@H:5]1[O:4][CH2:1][CH2:2][NH:27][C:28](=[O:37])[O:29][CH2:30][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1)(=[O:10])[CH3:9]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 280458benzyl N-(2-hydroxyethyl)carbamateHCID 11012995HCID 11012995, compound

Product 1

HCID 131736871HCID 131736871, compound

Reagents, catalysts & solvents 1

HCID 694302-OxopropiononitrileSolvent

Procedure

To a stirred solution of 1,2,3,4-tetra-O-acetyl-L-fucopyranose (200 g, 601.86 mmol) in AcCN (100 mL) and benzyl (2-hydroxyethyl)carbamate (140.96 g, 722.08 mmol) at 0° C. was added BF3.Et2O (427.7 g, 3.01 mol) dropwise over 2 hr. After stirring at rt for 16 hr, the reaction mixture was cooled to 0° C. and followed by the addition of Et3N (130 mL). The resulting mixture was concentrated and the residual was dissolved in CH2Cl2 (2.0 L), which was subsequently washed with sat. NaHCO3 (2×500 mL), water (2×500 mL) and brine (500 mL). The organic phase was separated, dried over Na2SO4, and concentrated. The residue was purified by flash chromatography on silica gel, eluting with EtOAc/petroleum ether (1:3) to give the title compound. 1H NMR (CDCl3) δ 7.33-7.37(5H, m), 5.12-5.32(5H, m), 4.99-5.04(1H, m), 4.42-4.45 (1H, d), 3.87-3.94 (1H, m), 3.78-3.84 (1H, m), 3.66-3.70(1H, m), 3.42-3.44 (2H, m), 2.19 (3H, s), 2.05-2.12(6H, m), 1.25-1.30 (3H, d).

Workup

  1. temperaturethe reaction mixture was cooled to 0° C.
  2. concentrationThe resulting mixture was concentrated
  3. dissolutionthe residual was dissolved in CH2Cl2 (2.0 L)
  4. washwhich was subsequently washed with sat. NaHCO3 (2×500 mL), water (2×500 mL) and brine (500 mL)
  5. customThe organic phase was separated
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel
  9. washeluting with EtOAc/petroleum ether (1:3)

Sources & evidence

ORD record
ord-7fd683512bcb4a30a520ca0c29de644a
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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