Ethyl Acetate → HCID 66899702, compound

HRID 2168516Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]2[C:8](=[C:9]([C:11]([O:13][CH3:14])=[O:12])[CH:10]=1)[N:7]([CH2:15][CH:16]([O:19][CH3:20])[O:17][CH3:18])[N:6]=[CH:5]2.[C:21](=O)([O-])[O-].[K+].[K+].CB1OB(C)OB(C)O1.C(OCC)(=O)C>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:18][O:17][CH:16]([O:19][CH3:20])[CH2:15][N:7]1[C:8]2[C:4](=[CH:3][C:2]([CH3:21])=[CH:10][C:9]=2[C:11]([O:13][CH3:14])=[O:12])[CH:5]=[N:6]1

Participants

Conditions

Temperature: 100 °C

Procedure

To methyl 5-bromo-1-(2,2-dimethoxyethyl)-1H-indazole-7-carboxylate from Step D of Example 10 in DMF (100 mL) was added potassium carbonate (622 mg, 4.5 mmol), tetrakis(triphenylphosphine)palladium(0) (347 mg, 0.3 mmol) and trimethylboroxine (377 mg, 3.0 mmol) and the reaction mixture was stirred at 100° C. for 24 h. Then another portion of trimethylboroxine (377 mg, 3 mmol) was added and the reaction was further stirred for 6 h. Ethyl acetate was added and the reaction was washed with water and concentrated in vacuo. The crude mixture was purified by column chromatography (silica gel, 0-30% ethyl acetate/hexanes) to afford methyl 1-(2,2-dimethoxyethyl)-5-methyl-1H-indazole-7-carboxylate (213 mg, 51%) as a white solid: 1H NMR (500 MHz, CDCl3) δ 8.00 (s, 1H), 7.73 (s, 1H), 7.65 (s, 1H), 4.92 (d, J=5.5 Hz, 2H), 4.54 (t, J=5.5 Hz, 1H), 3.98 (s, 3H), 3.28 (s, 6H), 2.47 (s, 3H); MS (ESI+) m/z 279 (M+H).

Workup

stirringthe reaction was further stirred for 6 h
washthe reaction was washed with water
concentrationconcentrated in vacuo
customThe crude mixture was purified by column chromatography (silica gel, 0-30% ethyl acetate/hexanes)

Sources & evidence

ORD record: ord-5c977985bdcf440fad08150edb6be5bb
Source dataset: uspto-grants-2015_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09045501B2

Reaction notes

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