Oxygen → HCID 22349426, compound

HRID 896022Notes

Reaction equation

HRID 896022 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]([O:7][C:8]2[CH:9]=[C:10]3[C:14](=[CH:15][CH:16]=2)[NH:13][N:12]=[CH:11]3)=[CH:5][CH:4]=1.O=O.[N:21]1[CH:26]=[CH:25][CH:24]=[C:23](B(O)O)[CH:22]=1.[N:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.CS(C)=O>[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]([O:7][C:8]2[CH:9]=[C:10]3[C:14](=[CH:15][CH:16]=2)[N:13]([C:23]2[CH:22]=[N:21][CH:26]=[CH:25][CH:24]=2)[N:12]=[CH:11]3)=[CH:5][CH:4]=1.[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6]([O:7][C:8]2[CH:16]=[CH:15][C:14]3[C:10](=[CH:11][N:12]([C:32]4[CH:31]=[N:30][CH:35]=[CH:34][CH:33]=4)[N:13]=3)[CH:9]=2)=[CH:5][CH:4]=1

Participants

9

Reactant 4

HCID 977OxygenHCID 1049PyridineHCID 27343783-Pyridinylboronic acidHCID 223494441H-Indazole, 5-(4-methoxyphenoxy)-

Product 2

HCID 22349426HCID 22349426, compoundHCID 22349446HCID 22349446, compound

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Procedure

A mixture of 5-(4-methoxy-phenoxy)-1H-indazole (0.20 grams, 0.83 mmol) and 1.7 mL of anhydrous dimethyl sulfoxide (previously saturated with oxygen) was treated with 3-pyridylboronic acid (0.25 grams, 1.7 mmol), copper (II) acetate (0.23 grams, 1.2 mmol), pyridine (0.34 mL, 0.33 grams, 4.2 mmol) and 4A molecular sieves (0.17 grams). After stirring for 14 days under an oxygen atmosphere, the mixture was diluted with water, extracted 3 times with ethyl acetate, and the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography eluting with ethyl acetate-hexanes (0-100%), affording 5-(4-Methoxy-phenoxy)-1-pyridin-3-yl-1H-indazole (0.11 grams) (1H NMR (CDCl3, 400 MHz): δ 9.07 (d, 1H, J=2.1 Hz), 8.60 (d, 1H, J=4.2 Hz), 8.12 (s, 1H), 8.10 (dd, 1H, J=1.3, 5.8 Hz), 7.65 (dd, 1H, J=1.1, 9.6 Hz), 7.50 (dd, 1H, J=5.0, 8.3 Hz), 7.25 (m, 2H), 7.00-6.80 (m, 5H), 3.80 (s, 3H) ppm) and 5-(4-Methoxy-phenoxy)-2-pyridin-3-yl-2H-indazole (0.050 grams) (1H NMR (CDCl3, 400 MHz): δ 9.12 (bs, 1H), 8.50 (b, 1H), 8.32 (d, 1H, J=8.3 Hz), 8.29 (s, 1H), 7.73 (d\d, 1H, J=9.5 Hz), 7.54 (dd, 1H, J=4.6, 7.9 Hz), 7.16 (dd, 1H, J=2.1, 9.1 Hz), 7.01 (d, 2H, J=9.1 Hz), 6.96 (s, 1H), 6.90 (d, 2H, J=8.7 Hz), 3.81 (s, 3H) ppm) as colorless syrups.

Workup

  1. extractionextracted 3 times with ethyl acetate
  2. dry with materialthe combined organic layers were dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography
  6. washeluting with ethyl acetate-hexanes (0-100%)

Sources & evidence

ORD record
ord-0935415738bf49a183222fee69962216
Source dataset
uspto-grants-2005_07
Patent number
US06919332B2

Reaction notes

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