Acetate → Methyl 1-cyclopropyl-1H-indazole-5-carboxylate

HRID 73106Notes

Reaction equation

HRID 73106 reaction equation
[NH:1]1[C:9]2[C:4](=[CH:5][C:6]([C:10]([O:12][CH3:13])=[O:11])=[CH:7][CH:8]=2)[CH:3]=[N:2]1.[CH:14]1(B(O)O)[CH2:16][CH2:15]1.C([O-])(=O)C.N1C=CC=CC=1C1C=CC=CN=1.[NH4+].[Cl-]>ClCCCl.O.C(Cl)Cl>[CH:14]1([N:1]2[C:9]3[C:4](=[CH:5][C:6]([C:10]([O:12][CH3:13])=[O:11])=[CH:7][CH:8]=3)[CH:3]=[N:2]2)[CH2:16][CH2:15]1

Participants

9

Reactant 5

HCID 175AcetateHCID 14742,2'-BipyridineHCID 25517Ammonium ChlorideHCID 2760897Cyclopropylboronic acidHCID 22260640Methyl 1H-indazole-5-carboxylate

Product 1

HCID 66837925Methyl 1-cyclopropyl-1H-indazole-5-carboxylateYield 71%

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of methyl 1H-indazole-5-carboxylate (970 mg, 5.5 mmol), cyclopropylboronic acid (946 mg, 11 mmol), cupper (II) acetate, [2,2′]bipyridyl (860 mg, 5.5 mmol) in 1,2-dichloroethane (50 mL) was heated at 70° C. for 2 hrs. The mixture was added saturated aqueous NH4Cl (70 mL) followed by the addition of DCM (30 mL) and water (30 mL), extracted with DCM (30 mL×2), dried over Na2SO4, filtered through a pad of Celite (registered trademark) the filtrate was concentrated to give a pale brown solid, which was purified by column chromatography on silica gel (hexane/EtOAc=8/1) to give 840 mg (71% yield) of the titled compound as a off-white solid.

Workup

  1. extractionextracted with DCM (30 mL×2)
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered through a pad of Celite (registered trademark) the filtrate
  4. concentrationwas concentrated
  5. customto give a pale brown solid, which
  6. customwas purified by column chromatography on silica gel (hexane/EtOAc=8/1)

Sources & evidence

ORD record
ord-8b8ee746670a46bca818e03d9111367f
Source dataset
uspto-grants-2014_09
Patent number
US08829026B2

Reaction notes

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