Sodium Carbonate → HCID 76695337, compound

HRID 1868343Notes

Reaction equation

HRID 1868343 reaction equation
Br[C:2]1[C:3]([CH:15]=[O:16])=[N:4][N:5]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=1.CC1(C)C(C)(C)OB([CH:25]=[CH:26][C:27]2[CH:28]=[N:29][CH:30]=[CH:31][CH:32]=2)O1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.O.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]>[N:29]1[CH:30]=[CH:31][CH:32]=[C:27]([CH:26]=[CH:25][C:2]2[C:3]([CH:15]=[O:16])=[N:4][N:5]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=2)[CH:28]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 57982717HCID 57982717, compoundHCID 667342383-[2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-YL)-vinyl]-pyridine

Product 1

HCID 76695337HCID 76695337, compound

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

After the solution of 4-bromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazole-3-carbaldehyde Compound 3a (570 mg, 1.87 mmol) and 3-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-vinyl]-pyridine Compound 3c (863 mg, 3.74 mmol) in dioxane (35 mL) was degassed by evacuating and purging with nitrogen. [1,1′-Bis(diphenylphosphino)-ferrocene]dichloropalladium(II) complex (Pd(dppf)2Cl2) (273 mg, 0.374 mmol) and sodium carbonate in water (3.74 mL, 2M) were added to the reaction mixture. The resultant suspension was purged again with nitrogen and heated at 120° C. for 30 min in a microwave reactor. After the solvent was removed in vacuo, the residue was dissolved in methanol and loaded to silica gel directly. The crude compound was eluted with a gradient of 4:1 to 2:1 hexane/ethyl acetate by flush chromatography to yield 4-(2-pyridin-3-yl-vinyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazole-3-carbaldehyde Compound 3d (385.6 mg, 0.624 mmol, 72% yield) as a white solid. 1H NMR (300 MHz, CDCl3) δ 10.26 (s, 1H), 8.75 (s, 1H), 8.55 (d, 1H), 7.91 (m, 3H), 7.54 (d, 1H), 7.50 (t, 2H), 7.34 (dd, 2H), 7.11 (d, 1H), 5.82 (s, 2H), 3.62 (t, 2H), 0.94 (t, 2H), 0 (s, 9H); MS (ESI) m/z: 330.1 (M+H+).

Workup

  1. customby evacuating
  2. custompurging with nitrogen
  3. customThe resultant suspension was purged again with nitrogen
  4. customAfter the solvent was removed in vacuo
  5. dissolutionthe residue was dissolved in methanol
  6. washThe crude compound was eluted with a gradient of 4:1 to 2:1 hexane/ethyl acetate
  7. customby flush chromatography

Sources & evidence

ORD record
ord-29ced1bcafd943899af28d4e043b491e
Source dataset
uspto-grants-2009_12
Patent number
US07635703B2

Reaction notes

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