Pivaloyl chloride → HCID 10941025, compound

HRID 1637431Notes

Reaction equation

HRID 1637431 reaction equation
[O:1]=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([CH2:11][OH:12])[OH:10])[OH:8])[OH:6])[OH:4].[C:13](Cl)(=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15]>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[C:13]([O:1][C@@H:2]1[O:10][C@H:9]([CH2:11][O:12][C:13](=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15])[C@@H:7]([O:8][C:13](=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15])[C@H:5]([O:6][C:13](=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15])[C@H:3]1[O:4][C:13](=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15]

Participants

5

Reactant 2

HCID 62493Pivaloyl chlorideHCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

Product 1

HCID 10941025HCID 10941025, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of D-glucose 42 (500 mg, 2.77 mmol) in 25 mL of pyridine is added pivaloyl chloride (3.42 mL, 3.34 g, 27.75 mmol) followed by DMAP (34 mg, 0.27 mmol). The reaction mixture is heated at 100° C. for 12 h, cooled to room temperature and quenched with 2 mL methanol. The reaction mixture is concentrated and the resulting residue is taken up in 25 mL CH2Cl2, washed with 1N HCl (3×25 mL), saturated NaCl (25 mL), dried over Na2SO4, filtered, concentrated and purified by flash chromatography (10% EtOAc/hexane) to afford 1.49 g (90%) of 1,2,3,4,6-penta-O-pivaloyl-β-D-glucopyranose 43: Rf 0.18 (5% EtOAc/hexane); 1H NMR (CDCl3, 270 MHz) δ 5.69 (d, J=8.2 Hz, 1H, H-1), 5.37 (app t, J=9.2 Hz, 1H, H-3), 5.21 (app t, J=8.7 Hz, 1H, H-4), 5.16 (app t, J=9.5 Hz, 1H, H-2), 4.06-4.17 (m, 2H, H-6), 3.86 (ddd, J=9.8, 4.8, 2.3 Hz, 1H, H-5), 1.21 (s, 9H), 1.17 (s, 9H), 1.15 (s, 9H), 1.12 (s, 18H).

Workup

  1. temperaturecooled to room temperature
  2. customquenched with 2 mL methanol
  3. concentrationThe reaction mixture is concentrated
  4. washwashed with 1N HCl (3×25 mL), saturated NaCl (25 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by flash chromatography (10% EtOAc/hexane)

Sources & evidence

ORD record
ord-bd94be1b3ab048d187b13d3aa2f71520
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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