Water → HCID 86664790, compound

HRID 1913241Notes

Reaction equation

HRID 1913241 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[C:3]([C:11]2[CH:12]=[N:13][N:14]3[C:19]([N:20]([CH2:29][O:30][CH2:31][CH2:32][Si:33]([CH3:36])([CH3:35])[CH3:34])[CH2:21][O:22][CH2:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])=[CH:18][C:17]([CH:37]=C)=[N:16][C:15]=23)[CH:2]=1.N1C(C)=CC=CC=1C.O.[O-:48]S([O-])(=S)=O.[Na+].[Na+]>O1CCOCC1.O=[Os](=O)(=O)=O>[CH3:36][Si:33]([CH3:34])([CH3:35])[CH2:32][CH2:31][O:30][CH2:29][N:20]([CH2:21][O:22][CH2:23][CH2:24][Si:25]([CH3:26])([CH3:27])[CH3:28])[C:19]1[N:14]2[N:13]=[CH:12][C:11]([C:3]3[CH:2]=[N:1][C:10]4[C:5]([CH:4]=3)=[CH:6][CH:7]=[CH:8][CH:9]=4)=[C:15]2[N:16]=[C:17]([CH:37]=[O:48])[CH:18]=1

Participants

7

Reactant 4

HCID 962WaterHCID 79372,6-LutidineHCID 24477Sodium ThiosulfateHCID 66733437HCID 66733437, compound

Product 1

HCID 86664790HCID 86664790, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 312751,4-DioxaneSolvent2×

Procedure

To 3-(quinolin-3-yl)-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)-5-vinylpyrazolo[1,5-a]pyrimidin-7-amine (Int-8a, 0.7 g, 1.3 mmol) in 1,4-dioxane (10 mL) was added 2.5 wt % OsO4 in 1,4-dioxane (1.0 g, 0.02 mmol), 2,6-lutidine (0.6 mL, 5.2 mmol) and H2O (2 mL), and the resulting mixture was stirred at room temperature for 20 minutes. NaIO4 (0.8 g, 3.81 mmol) was then added and the reaction mixture was stirred at room temperature for 16 hours. L C/MS analysis at that time showed the diol intermediate was still present. Therefore, more NaIO4 (0.3 g, 1.3 mmol) was added, and the reaction mixture was stirred for 12 hours for full conversion to the product. Saturated Na2S2O3 solution (10 mL) was added and the mixture was stirred for 10 minutes. The organics were then extracted with CH2Cl2 (4×40 mL), dried (Na2SO4) and concentrated in vacuo to give 7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-3-(quinolin-3-yl)pyrazolo[1,5-a]pyrimidine-5-carbaldehyde (Int-8b) as a yellow solid (0.6 g, 1.2 mmol, 92%). LCMS: 2.67 mins, m/z=550.0 (MH+).

Workup

  1. stirringthe reaction mixture was stirred at room temperature for 16 hours
  2. stirringthe reaction mixture was stirred for 12 hours for full conversion to the product
  3. stirringthe mixture was stirred for 10 minutes
  4. extractionThe organics were then extracted with CH2Cl2 (4×40 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ced4db7a85514a458ca4f6d304b9f638
Source dataset
uspto-grants-2013_12
Patent number
US08609675B2

Reaction notes

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