3,3-Diethoxy-1-propene → HCID 68546003, compound

HRID 1446658Notes

Reaction equation

HRID 1446658 reaction equation
B1C2CCCC1CCC2.[CH2:10]([O:12][CH:13]([O:16][CH2:17][CH3:18])[CH:14]=[CH2:15])[CH3:11].Cl[C:20]1[CH:25]=[C:24]([C:26]2[CH:31]=[CH:30][N:29]3[CH:32]=[CH:33][N:34]=[C:28]3[CH:27]=2)[CH:23]=[CH:22][N:21]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>O.O1CCOCC1>[CH2:10]([O:12][CH:13]([O:16][CH2:17][CH3:18])[CH2:14][CH2:15][C:22]1[CH:23]=[C:24]([C:26]2[CH:31]=[CH:30][N:29]3[CH:32]=[CH:33][N:34]=[C:28]3[CH:27]=2)[CH:25]=[CH:20][N:21]=1)[CH3:11]

Participants

8

Reactant 5

HCID 624773,3-Diethoxy-1-propeneHCID 62657Potassium Phosphate, TribasicHCID 789669-Borabicyclo(3.3.1)nonaneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 76849533HCID 76849533, compound

Product 1

HCID 68546003HCID 68546003, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

In a round bottomed flask, add 9-BBN (0.5 M in THF, 42.2 mL, 2 equiv.) under nitrogen. Add acrolein diethyl acetal (3.4 mL, 2.1 equiv.) via syringe and stir at room temperature overnight. In a separate flask on the second day, combine 7-(2-chloro-pyridin-4-yl)-imidazo[1,2-a]pyridine (2.42 g, 11 mmol), potassium phosphate (4.47 g, 2 equiv.), S-Phos (0.54 g, 12.5 mol %), dioxane (90 mL), and water (45 mL). De-gas with nitrogen then add palladium (II) acetate (0.118 g, 5 mol %) under nitrogen. To this solution add the material from the first flask via canula. Heat the reaction at 80° C. for 5.5 hours. Concentrate to dryness. Slurry in DCM then filter to remove insoluble material. Wash with DCM. Concentrate filtrate and purify by silica plug (1:1 Hexanes:Ethyl Acetate→Ethyl Acetate→5% Methanol:DCM→10% Methanol:DCM) to give a residue (4.15 g, >100%) which is used as is for the next step. MS (ES), m/z 326 (M+1).

Workup

  1. customIn a separate flask on the second day, combine
  2. customDe-gas with nitrogen
  3. additionTo this solution add the material from the first flask via canula
  4. temperatureHeat
  5. customthe reaction at 80° C. for 5.5 hours
  6. concentrationConcentrate to dryness
  7. filtrationthen filter
  8. customto remove insoluble material
  9. washWash with DCM
  10. customConcentrate filtrate and purify by silica plug (1:1 Hexanes:Ethyl Acetate→Ethyl Acetate→5% Methanol:DCM→10% Methanol:DCM)

Sources & evidence

ORD record
ord-f8067352c88048dcaf18497f7912f15d
Source dataset
uspto-grants-2010_02
Patent number
US07666879B2

Reaction notes

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