Propargyl alcohol → HCID 11211349, compound

HRID 2206940Notes

Reaction equation

HRID 2206940 reaction equation
B(F)(F)F.[CH3:5][CH2:6][O:7]CC.[C:10]([O:13][C@H:14]1[O:31][C@H:30]([CH2:32][O:33][C:34](=O)[CH3:35])[C@@H:25]([O:26][C:27](=[O:29])[CH3:28])[C@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@@H:15]1[O:16]C(=O)C)(=[O:12])[CH3:11].[CH2:37](O)C#C.C(=O)([O-])[O-].[K+].[K+]>ClCCl>[C:6]([O:31][C@H:30]1[C@@H:25]([O:26][C:27](=[O:29])[CH3:28])[C@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@@H:15]([CH2:14][O:13][C:10](=[O:12])[CH3:11])[O:16][C@@H:32]1[O:33][CH2:34][C:35]#[CH:37])(=[O:7])[CH3:5]

Participants

6

Reactant 4

HCID 7859Propargyl alcoholHCID 8000Boron trifluoride etherateHCID 11430Potassium CarbonateHCID 11741089α-D-Mannose pentaacetate

Product 1

HCID 11211349HCID 11211349, compoundYield 100.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Under nitrogen atmosphere, boron trifluoride ethyl etherate (7.90 mL, 64 mmol, 5 equiv) was added dropewise at 0° C. to a solution of α-D-mannopyranose pentaacetate (5 g, 12.8 mmol) and propargyl alcohol (2.98 mL, 51.2 mmol, 4 equiv) in anhydrous dichloromethane (150 mL) and the solution was stirred at 0° C. for 4 days. Anhydrous potassium carbonate (8 g) was added and the reaction mixture was stirred for further 1 h and filtered. The filtrate was diluted with dichloromethane (200 mL), washed with water (3×200 mL), dried over Na2SO4, filtered and concentrated to afford 2-propynyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside (4.95 g, quantitative yield) as a brown oil which was used without further purification. 1H NMR (400 MHz, CDCl3): δ=5.38-5.20 (m, 3H, H2,3,4), 5.02 (d, J=1.6 Hz, 1H, H1), 4.27 (dd, J=5.2, 12.2 Hz, 1H, H6), 4.26 (d, J=2.4 Hz, 2H, OCH2C≡CH), 4.10 (dd, J=2.5, 12.2 Hz, 1H, H6), 4.45-3.72 (m, 1H, H5), 2.46 (t, J=2.4 Hz, 1H, C≡CH), 2.15, 2.09, 2.03, 1.98 (4s, 4×3H, OCOCH3); 13C NMR (100.6 MHz, CDCl3): δ=170.7, 170.0, 169.9 and 169.8 (OCOCH3), 96.4 (CO, 78.0 (C≡C—H), 75.7 (C≡C—H), 69.5 (C5), 69.1 (C4), 69.0 (C3), 66.2 (C2), 62.5 (C6), 55.1 (OCH2C≡C—H), 20.9, 20.8×2 and 20.7 (OCOCH3); MS (ESI): m/z=409.0 [M+Na]+.

Workup

  1. stirringthe reaction mixture was stirred for further 1 h
  2. filtrationfiltered
  3. additionThe filtrate was diluted with dichloromethane (200 mL)
  4. washwashed with water (3×200 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-67d1dc4731004c749c6405c13a087d87
Source dataset
uspto-grants-2016_06
Patent number
US09375472B2

Reaction notes

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