Methyl morpholine oxide → HCID 117996221, compound

HRID 1488300Notes

Reaction equation

HRID 1488300 reaction equation
[C:1]([O:4][C@H:5]1[C@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C:20](=[O:22])[CH3:21])[C@H:12]([CH3:23])[O:11][C@H:6]1[O:7][CH2:8][CH:9]=C)(=[O:3])[CH3:2].C[N+]1([O-])CC[O:28]CC1>CC(C)=O.O.O=[Os](=O)(=O)=O.C(O)(C)(C)C>[C:1]([O:4][C@H:5]1[C@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C:20](=[O:22])[CH3:21])[C@H:12]([CH3:23])[O:11][C@H:6]1[O:7][CH2:8][CH:9]=[O:28])(=[O:3])[CH3:2]

Participants

7

Reactant 2

HCID 82029Methyl morpholine oxideHCID 117996440HCID 117996440, compound

Product 1

HCID 117996221HCID 117996221, compoundYield 49%

Reagents, catalysts & solvents 4

HCID 6386tert-ButanolCatalystHCID 30318Osmium TetroxideCatalystHCID 180AcetoneSolventHCID 962WaterSolvent2×

Procedure

To a solution of prop-2-en-1-yl 2,3,4-tri-O-acetyl-α-L-fucopyranoside (1.34 g, 4.06 mmol) in acetone (30 mL) and water (7.5 mL) was added 4-methylmorpholine 4-oxide (950 mg, 8.11 mmol) followed by the addition of 2.5% OsO4 in tert-butanol (2.04 mL, 0.162 mmol). The mixture was allowed to stir at rt for 16 hr. To the resulting mixture was then added a solution of NaIO4 (1.74 g, 8.11 mmol) in water (15 mL). After stirring for additional 4 hr, the precipitate was filtered and washed with acetone (50 mL). The volume of the filtrate was reduced to approximately ⅓ of the initial volume and then diluted with sat. NaHCO3 (100 mL). The mixture was extracted with EtOAc (3×50 mL). The organic phases were combined and washed with brine, dried over Na2SO4, and concentrated. The residue was purified by silica gel column chromatography (Teledyne Isco: 120 g), eluting with 0-80% EtOAc in hexanes to give the title compound (660 mg, 49%). 1H NMR (CDCl3) δ 9.72 (1H, s), 5.44 (1H, dd, J=10.9 and 3.3 Hz), 5.35 (1H, dd, J=3.4 and 1.8 Hz), 5.19 (1H, dd, J=10.9 and 3.8 Hz), 5.13 (1H, d, J=3.8 Hz), 4.26 (3H, m), 2.19 (3H, s), 2.15 (3H, s), 2.02 (3H, s), 1.17 (3H, d, J=6.6 Hz).

Workup

  1. stirringAfter stirring for additional 4 hr
  2. filtrationthe precipitate was filtered
  3. washwashed with acetone (50 mL)
  4. additiondiluted with sat. NaHCO3 (100 mL)
  5. extractionThe mixture was extracted with EtOAc (3×50 mL)
  6. washwashed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel column chromatography (Teledyne Isco: 120 g)
  10. washeluting with 0-80% EtOAc in hexanes

Sources & evidence

ORD record
ord-7b71830cc05b4850af22ddcdd2db3fdf
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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