Water → tert-Butyl 3-(3-{1-[4-amino-3-(1,2-dihydroxyethyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl]ethyl}-5-chloro-2-ethoxy-6-fluorophenyl)azetidine-1-carboxylate

HRID 1499811Notes

Reaction equation

HRID 1499811 reaction equation
[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([CH:13]([C:15]3[C:16]([O:34][CH2:35][CH3:36])=[C:17]([CH:23]4[CH2:26][N:25]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:24]4)[C:18]([F:22])=[C:19]([Cl:21])[CH:20]=3)[CH3:14])[N:9]=[C:10]([CH:11]=[CH2:12])[C:3]=12.C[N+]1([O-])CC[O:41]CC1.[OH2:45].CCOC(C)=O>C(O)(C)(C)C.[Os](=O)(=O)(=O)=O>[NH2:1][C:2]1[N:7]=[CH:6][N:5]=[C:4]2[N:8]([CH:13]([C:15]3[C:16]([O:34][CH2:35][CH3:36])=[C:17]([CH:23]4[CH2:24][N:25]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:26]4)[C:18]([F:22])=[C:19]([Cl:21])[CH:20]=3)[CH3:14])[N:9]=[C:10]([CH:11]([OH:41])[CH2:12][OH:45])[C:3]=12

Participants

7

Reactant 4

HCID 962Water2×HCID 8857Ethyl AcetateHCID 82029Methyl morpholine oxideHCID 86677734tert-Butyl 3-{3-[1-(4-amino-3-vinyl-1H-pyrazolo[3,4-d]pyrimidin-1-yl)ethyl]-5-chloro-2-ethoxy-6-fluorophenyl}azetidine-1-carboxylate

Product 1

HCID 86677735tert-Butyl 3-(3-{1-[4-amino-3-(1,2-dihydroxyethyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl]ethyl}-5-chloro-2-ethoxy-6-fluorophenyl)azetidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 6386tert-ButanolSolvent

Procedure

To a suspension of tert-butyl 3-{3-[1-(4-amino-3-vinyl-1H-pyrazolo[3,4-d]pyrimidin-1-yl)ethyl]-5-chloro-2-ethoxy-6-fluorophenyl}azetidine-1-carboxylate (0.707 g, 1.37 mmol) in tert-butyl alcohol (8.6 mL) was added N-methylmorpholine N-oxide (176 mg, 1.50 mmol), water (4.3 mL), and osmium tetraoxide (20 mg, 0.080 mmol). The resulting mixture was stirred overnight at room temperature. Water was added to the reaction followed by EtOAc. The layers were separated and the aqueous extracted with EtOAc. The combined organics were washed with brine, dried over Na2SO4, filtered, and concentrated to give the crude product. LCMS calculated for C25H33ClFN6O5 (M+H)+: m/z=551.2; Found:551.2.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous extracted with EtOAc
  3. washThe combined organics were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-5cf68b7a282b4ea58dc169a25a0ccfde
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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