Allyl Isothiocyanate → (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-allylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

HRID 2194655Notes

Reaction equation

HRID 2194655 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([N:11]=[C:12]=[S:13])[C@@H:9]([O:14][C:15](=[O:17])[CH3:16])[C@H:8]([O:18][C:19](=[O:21])[CH3:20])[C@@H:7]([CH2:22][O:23][C:24](=[O:26])[CH3:25])[O:6]1)(=[O:3])[CH3:2].[N:27]([CH2:30][CH:31]=[CH2:32])=C=S>CC#N>[C:1]([O:4][C@H:5]1[C@H:10]([NH:11][C:12]([NH:27][CH2:30][CH:31]=[CH2:32])=[S:13])[C@@H:9]([O:14][C:15](=[O:17])[CH3:16])[C@H:8]([O:18][C:19](=[O:21])[CH3:20])[C@@H:7]([CH2:22][O:23][C:24](=[O:26])[CH3:25])[O:6]1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 5971Allyl IsothiocyanateHCID 14130735(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-isothiocyanatotetrahydro-2H-pyran-2,4,5-triyl triacetate

Product 1

HCID 10388857(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-allylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetateYield 81%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a stirred solution of (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-isothiocyanato-tetrahydro-2H-pyran-2,4,5-triyl triacetate (0.50 g, 1.31 mmol) in CH3CN, was added neat 3-isothiocyanatoprop-1-ene (0.155 g, 1.2 mmol), dropwise. The reaction was stirred at room temperature until complete by TLC (3 h). The reaction was washed with a minimal amount of saturated aqueous NaHCO3 (15 mL). The aqueous layer was then extracted three times with DCM, and the organic layers were combined, dried with MgSO4, filtered and concentrated. The concentrated mixture was purified via flash column chromatography in a solvent system of 1:1 EtOAc and hexanes, providing (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-allylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate (0.410 g, 81% yield) 1H NMR (500 MHz, CDCl3) δ 1.98 (s, 3H), 2.00 (s, 3H), 2.03 (s, 3H), 2.05 (s, 3H), 3.81-3.83 (m, 1H), 4.02-4.08 (m, 3H), 4.21 (dd, 1H, J=4.6, 12.5 Hz), 5.06-5.15 (m, 3H), 5.20-5.30 (m, 2H), 5.72 (d, 1H, J=8.6 Hz), 5.75-5.8 (s, 1H), 6.42-6.52 (m, 2H).

Workup

  1. washThe reaction was washed with a minimal amount of saturated aqueous NaHCO3 (15 mL)
  2. extractionThe aqueous layer was then extracted three times with DCM
  3. dry with materialdried with MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe concentrated mixture was purified via flash column chromatography in a solvent system of 1:1 EtOAc and hexanes

Sources & evidence

ORD record
ord-aa56f43439dc41de8b37b3376ae96456
Source dataset
uspto-grants-2012_12
Patent number
US08334310B2

Reaction notes

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