Triethylamine → (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-ethylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

HRID 2194652Notes

Reaction equation

HRID 2194652 reaction equation
Cl.[C:2]([O:5][C@H:6]1[C@H:11]([NH2:12])[C@@H:10]([O:13][C:14](=[O:16])[CH3:15])[C@H:9]([O:17][C:18](=[O:20])[CH3:19])[C@@H:8]([CH2:21][O:22][C:23](=[O:25])[CH3:24])[O:7]1)(=[O:4])[CH3:3].[CH2:26]([N:28]=[C:29]=[S:30])[CH3:27].C(N(CC)CC)C>CC#N>[C:2]([O:5][C@H:6]1[C@H:11]([NH:12][C:29]([NH:28][CH2:26][CH3:27])=[S:30])[C@@H:10]([O:13][C:14](=[O:16])[CH3:15])[C@H:9]([O:17][C:18](=[O:20])[CH3:19])[C@@H:8]([CH2:21][O:22][C:23](=[O:25])[CH3:24])[O:7]1)(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 10966Ethyl isothiocyanateHCID 20225910034-20-5

Product 1

HCID 24808482(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-ethylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a suspension of (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-amino-tetrahydro-2H-pyran-2,4,5-triyl triacetate hydrochloride (2.04 g, 5.19 mmol) in CH3CN (80 mL) was added ethyl isothiocyanate (1.36 g, 15.57 mmol), followed by triethylamine (0.94 g, 9.31 mmol). The reaction mixture was heated to reflux and stirred for 3 h. The organic layer was concentrated, and redissolved in CH2Cl2. The reaction was then washed with a minimal amount of saturated aqueous NaHCO3 solution. The aqueous layer was extracted an additional two times with CH2Cl2. The organic layer was dried (MgSO4), filtered, and concentrated in vacuo. The desired (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-ethylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate was obtained as a yellow oil (2.21 g, 98% yield) following flash chromatography (EtOAc/hexanes, 1:1). 1H NMR (500 MHz, CDCl3) δ 1.19 (m, 3H), 1.81 (d, 1H, J=4.0 Hz), 2.05 (s, 3H), 2.08 (s, 3H), 2.10 (s, 3H), 2.14 (s, 3H), 3.40 (s, 1H), 3.85 (m, 1H), 4.12 (m, 1H), 4.28 (m, 1H), 4.81 (s, 1H), 5.19 (m, 1H), 5.73 (d, 1H, J=7.7 Hz), 6.00 (s, 1H), 6.12 (d, 1H, J=15.0 Hz); 13C NMR (125 MHz, CDCl3) δ 14.39, 20.81, 20.96, 21.07, 21.25, 57.84, 60.67, 61.95, 68.08, 72.99, 73.31, 93.12, 163.03, 169.60, 170.97, 171.88.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux
  3. concentrationThe organic layer was concentrated
  4. dissolutionredissolved in CH2Cl2
  5. washThe reaction was then washed with a minimal amount of saturated aqueous NaHCO3 solution
  6. extractionThe aqueous layer was extracted an additional two times with CH2Cl2
  7. dry with materialThe organic layer was dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-fb0b3d89367246acb3529ebd357ff640
Source dataset
uspto-grants-2012_12
Patent number
US08334310B2

Reaction notes

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