Acetone → HCID 58382060, compound

HRID 1628045Notes

Reaction equation

HRID 1628045 reaction equation
[CH3:1][C:2]1([C:7]2[CH:12]=[CH:11][C:10]([C:13]3[N:33]([CH2:34][O:35][CH2:36][CH2:37][Si:38]([CH3:41])([CH3:40])[CH3:39])[C:16]4=[N:17][CH:18]=[C:19]([N:21]([CH2:29][C:30]([CH3:32])=C)[C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[N:20]=[C:15]4[CH:14]=3)=[CH:9][CH:8]=2)[O:6][CH2:5][CH2:4][O:3]1.CC[O:44]C(C)=O.CC(C)=O>O1CCOCC1.O.O=[Os](=O)(=O)=O>[CH3:1][C:2]1([C:7]2[CH:8]=[CH:9][C:10]([C:13]3[N:33]([CH2:34][O:35][CH2:36][CH2:37][Si:38]([CH3:40])([CH3:39])[CH3:41])[C:16]4=[N:17][CH:18]=[C:19]([N:21]([CH2:29][C:30](=[O:44])[CH3:32])[C:22](=[O:28])[O:23][C:24]([CH3:26])([CH3:25])[CH3:27])[N:20]=[C:15]4[CH:14]=3)=[CH:11][CH:12]=2)[O:6][CH2:5][CH2:4][O:3]1

Participants

7

Reactant 3

HCID 180AcetoneHCID 8857Ethyl Acetate2×HCID 58382377HCID 58382377, compound

Product 1

HCID 58382060HCID 58382060, compoundYield 86%

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalyst2×HCID 962WaterSolvent4×HCID 312751,4-DioxaneSolvent

Procedure

tert-Butyl 6-(4-(2-methyl-1,3-dioxolan-2-yl)phenyl)-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazin-2-yl(2-methylallyl)carbamate (0.55 g, 0.95 mmol) and NaIO4 (0.194 mL, 3.79 mmol) were combined in a mixture of 1,4-dioxane (14.0 mL) and water (4.9 mL). To the mixture was added OsO4 (2.5 wt % in t-BuOH, 0.475 mL, 0.038 mmol) and the mixture stirred for about 6 h at rt. EtOAc (50 mL) and water (30 mL) were added and the layers separated. The aqueous layer was extracted with EtOAc (20 mL). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography (40 g Redi-Sep™ silica gel) eluting with 50-100% EtOAc/heptane. The mixture was added to NaIO4 (0.194 mL, 3.79 mmol), acetone (14.0 mL) and water (4.9 mL). To the mixture was added OsO4 (2.5 wt % in t-BuOH, 0.475 mL, 0.038 mmol) and the mixture stirred for about 3 h at rt. EtOAc (50 mL) and water (30 mL) were added and the layers separated. The organic layer was washed with brine (10 mL), dried over MgSO4, filtered, and concentrated in vacuo to give tert-butyl 6-(4-(2-methyl-1,3-dioxolan-2-yl)phenyl)-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazin-2-yl(2-oxopropyl)carbamate (0.473 g, 86%): LC/MS (Table 2, Method h) Rt=2.05 min.; MS m/z: 583 (M+H)+.

Workup

  1. customthe layers separated
  2. extractionThe aqueous layer was extracted with EtOAc (20 mL)
  3. washThe combined organic layers were washed with brine (10 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash column chromatography (40 g Redi-Sep™ silica gel)
  8. washeluting with 50-100% EtOAc/heptane
  9. stirringthe mixture stirred for about 3 h at rt
  10. customthe layers separated
  11. washThe organic layer was washed with brine (10 mL)
  12. dry with materialdried over MgSO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f24699e5d85d42818e79478ea7280a58
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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