Dichloromethane → HCID 90030064, compound

HRID 1488148Notes

Reaction equation

HRID 1488148 reaction equation
[CH3:1][C:2]1[CH:11]=[C:10]([CH3:12])[C:9](B2OC(C)(C)C(C)(C)O2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].I[C:23]1[N:27]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:35])([CH3:34])[CH3:33])[N:26]=[CH:25][C:24]=1[CH3:36].C([O-])([O-])=O.[K+].[K+].C(Cl)Cl>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][C:2]1[CH:11]=[C:10]([CH3:12])[C:9]([C:23]2[N:27]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:35])([CH3:34])[CH3:33])[N:26]=[CH:25][C:24]=2[CH3:36])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 59224686Methyl 2,4-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate2×HCID 90029660HCID 90029660, compound2×

Product 1

HCID 90030064HCID 90030064, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
90 °C

Procedure

Methyl 2,4-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (compound 160.1, 2.7 g, 9.32 mmol), 5-iodo-4-methyl-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazole (compound 250.2, 3.15 g, 9.32 mmol), K2CO3 (6.42 g, 46.6 mmol) and PdCl2(dppf).CH2Cl2 (0.76 g, 0.93 mmol) were added to a round bottom flask. The flask was purged with argon, then dioxane (50 mL) and water (20 mL) were added and the mixture was heated at 90° C. for 16 hours. The mixture was cooled to room temperature and then partitioned between EtOAc (300 mL) and water (50 mL). The organic layer was washed with brine (50 mL), dried (MgSO4) and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexanes:EtOAc, 10:11 to yield the title compound as a light brown oil (3.0 g, 86%). m/z (ES+) 375(M+H)+.

Workup

  1. customThe flask was purged with argon
  2. additiondioxane (50 mL) and water (20 mL) were added
  3. temperatureThe mixture was cooled to room temperature
  4. custompartitioned between EtOAc (300 mL) and water (50 mL)
  5. washThe organic layer was washed with brine (50 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (hexanes

Sources & evidence

ORD record
ord-f9f86a8b48bb4b1b9051166a74401764
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

Loading…