Methyl morpholine oxide → HCID 117996772, compound

HRID 1488277Notes

Reaction equation

HRID 1488277 reaction equation
[C:1]([O:9][C@H:10]1[C@H:19]([O:20][C:21](=[O:28])[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@H:18]([O:29][C:30](=[O:37])[C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C@H:17]([CH3:38])[O:16][C@H:11]1[O:12][CH2:13][CH:14]=C)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[N+]1([O-])CC[O:43]CC1>CC(C)=O.O.O=[Os](=O)(=O)=O>[C:1]([O:9][C@H:10]1[C@H:19]([O:20][C:21](=[O:28])[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@H:18]([O:29][C:30](=[O:37])[C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C@H:17]([CH3:38])[O:16][C@H:11]1[O:12][CH2:13][CH:14]=[O:43])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 82029Methyl morpholine oxideHCID 117996281HCID 117996281, compound

Product 1

HCID 117996772HCID 117996772, compound

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 180AcetoneSolventHCID 962WaterSolvent3×

Procedure

To a solution of prop-2-en-1-yl 2,3,4-tri-O-benzoyl-α-L-fucopyranoside (6.06 g, 11.73 mmol) in acetone (94 mL) and water (23.5 mL) was added 4-methylmorpholine 4-oxide (2.75 g, 23.46 mmol) followed by the addition of 2.5% OsO4 in water (5.97 g, 0.587 mmol). The mixture was allowed to stir at rt for 16 hr. To the resulting mixture was then added a solution of NaIO4 (5.40 g, 23.46 mmol) in water (100 mL). After stirring for additional 6 hr, the precipitate was filtered and washed with acetone (200 mL). The volume of the filtrate was reduced to approximately ⅓ of the initial volume and then extracted with EtOAc (200 mL). The organic phase was separated, washed with sat. NaHCO3 (200 mL). The aqueous phase was extracted with EtOAc (3×100 mL). The organic phases were combined and washed with brine, dried over Na2SO4, and concentrated. The residue was purified by flash chromatography on silica gel (220 g), eluting with 0-100% EtOAc in hexanes to give the title compound. 1H NMR (CDCl3) δ 1.33-1.29 (3H, m), 3.27 (1H, s), 3.41 (1H, s), 4.35-4.31 (1H, m), 5.51-5.45 (1H, m), 5.75-5.69 (1H, m), 5.81 (1H, dd, J=13.91, 3.57), 6.05-5.98 (1H, m), 7.42 (2H, d, J=7.76), 7.53 (5H, d, J=8.61), 7.67-7.63 (2H, m), 7.84-7.81 (2H, m), 8.01 (2H, t, J=8.82), 8.14-8.12 (2H, m), 9.77-9.77 (1H, m).

Workup

  1. stirringAfter stirring for additional 6 hr
  2. filtrationthe precipitate was filtered
  3. washwashed with acetone (200 mL)
  4. extractionextracted with EtOAc (200 mL)
  5. customThe organic phase was separated
  6. washwashed with sat. NaHCO3 (200 mL)
  7. extractionThe aqueous phase was extracted with EtOAc (3×100 mL)
  8. washwashed with brine
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated
  11. customThe residue was purified by flash chromatography on silica gel (220 g)
  12. washeluting with 0-100% EtOAc in hexanes

Sources & evidence

ORD record
ord-cab87e0cf275454396470cad77357340
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

Loading…