Potassium Carbonate → 1-({3-[(Benzyloxy)methyl]oxetan-3-yl}methyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole

HRID 2279828Notes

Reaction equation

HRID 2279828 reaction equation
[CH3:1][C:2]1([CH3:14])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:10]=[N:11][NH:12][CH:13]=2)[O:3]1.S(OC)(O[CH2:19][C:20]1([CH2:24][O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH2:23][O:22][CH2:21]1)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.CCOC(C)=O>[CH2:26]([O:25][CH2:24][C:20]1([CH2:19][N:12]2[CH:13]=[C:9]([B:4]3[O:5][C:6]([CH3:7])([CH3:8])[C:2]([CH3:14])([CH3:1])[O:3]3)[CH:10]=[N:11]2)[CH2:23][O:22][CH2:21]1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 27740104-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 86697765{3-[(Benzyloxy)methyl]oxetan-3-yl}methyl methyl sulfate2×

Product 1

HCID 678131161-({3-[(Benzyloxy)methyl]oxetan-3-yl}methyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleYield 84%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 4-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)-1H-pyrazole (0.825 g, 4.25 mmol) and {3-[(benzyloxy)methyl]oxetan-3-yl}methyl methyl sulfate (Compound 44D, 1.35 g, 4.46 mmol) in DMF (3.90 mL) was charged with potassium carbonate (588 mg, 4.25 mmol) and allowed to stir at rt for 16 hrs. The reaction mixture was diluted with EtOAc and washed with brine (2×), dried over sodium sulfate, filtered and concentrated in vacuo and purified using a Teledyne ISCO Combiflash® Rf system [0→40% Acetone/Heptanes] to afford 1.37 g of the title compound (84%). 1H NMR (400 MHz, CD3OD) δ 7.76 (s, 1H), 7.66 (s, 1H), 7.25-7.37 (m, 5H), 4.67 (d, J=6.6 Hz, 2H), 4.48-4.52 (m, 4H), 4.42 (d, J=6.6 Hz, 2H), 3.45 (s, 2H), 1.20 (s, 12H). MS (ESI): m/z=385.20 [M+H]+. HPLC: tR=1.08 min (UPLC-TOF: polar—2 min).

Workup

  1. washwashed with brine (2×)
  2. dry with materialdried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. custompurified

Sources & evidence

ORD record
ord-e80e6374fd96468a84d904f68e041644
Source dataset
uspto-grants-2015_09
Patent number
US09133224B2

Reaction notes

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