Bis(pinacolato)diborane → HCID 68156823, compound

HRID 537486Notes

Reaction equation

HRID 537486 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:4]=1[N:10]1[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[N:11]1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)[O:20]1.OOS([O-])=O.[K+]>CO.CO.C1CC=CCCC=C1.C1CC=CCCC=C1.[Ir].[Ir].O>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([OH:20])[CH:6]=[C:5]([CH3:9])[C:4]=1[N:10]1[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[N:11]1

Participants

6

Reactant 3

HCID 2733548Bis(pinacolato)diboraneHCID 23707502Potassium hydroxy sulfiteHCID 68156690HCID 68156690, compound

Product 1

HCID 68156823HCID 68156823, compoundYield 33%

Reagents, catalysts & solvents 2

HCID 11735004HCID 11735004, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

To a flask containing 1-(2-methoxy-6-methylphenyl)-4-(trifluoromethyl)-1H-pyrazole (75.0 mg, 0.290 mmol) was added di-μ-methoxobis(1,5-cyclooctadiene)diiridium(I) (2.00 mg, 0.003 mmol), bis(pinacolato)diboron (75.2 mg, 0.290 mmol), 4,4′di-tert-butyl-2,2′-dipyridyl (1.60 mg, 0.006 mmol) and degassed methyl tert-butyl ether (1.50 mL). The resulting red solution was heated to 80° C. for 18 h and then at room temperature for 3 d. The reaction was concentrated. Acetone (0.980 mL) was added to provide a homogenous solution followed by an aqueous solution of oxone (180 mg, 0.290 mmol), 0.98 mL of water) dropwise over 2 min. The reaction was stirred at room temperature for 18 h. The reaction was then quenched with aqueous sodium bisulfate and extracted three times with methylene chloride. The combined organic layers were washed with brine and water. The organic layer was then dried over sodium sulfate, filtered, and concentrated. Purification by column chromatography (0-25% ethyl acetate in heptane), gave 3-methoxy-5-methyl-4-(4-(trifluoromethyl)-1H-pyrazol-1-yl)phenol (26.0 mg, 33%) as a solid. 1H NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.75-7.70 (m, 1H), 6.27 (dd, J=15.8, 2.5 Hz, 2H), 3.68 (s, 3H), 1.96 (s, 3H). MS (M+1): 273.2.

Workup

  1. customdegassed methyl tert-butyl ether (1.50 mL)
  2. concentrationThe reaction was concentrated
  3. additionAcetone (0.980 mL) was added
  4. customto provide a homogenous solution
  5. customdropwise over 2 min
  6. customThe reaction was then quenched with aqueous sodium bisulfate
  7. extractionextracted three times with methylene chloride
  8. washThe combined organic layers were washed with brine and water
  9. dry with materialThe organic layer was then dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by column chromatography (0-25% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-35d50dfbd7fe475d98148139074cf57b
Source dataset
uspto-grants-2014_10
Patent number
US08859591B2

Reaction notes

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