Methyl 4-(chlorocarbonyl)benzoate → HCID 67055356, compound

HRID 602994Notes

Reaction equation

HRID 602994 reaction equation
Cl[C:2]([C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=1)=[O:3].[C:14]([C:16]1[CH:17]=[C:18]([Zn]I)[CH:19]=[CH:20][CH:21]=1)#[N:15].[BH4-].[Na+]>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:14]([C:16]1[CH:21]=[C:20]([CH:2]([OH:3])[C:4]2[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=2)[CH:19]=[CH:18][CH:17]=1)#[N:15]

Participants

6

Reactant 3

HCID 81850Methyl 4-(chlorocarbonyl)benzoateHCID 4311764Sodium borohydrideHCID 178509889HCID 178509889, compound

Product 1

HCID 67055356HCID 67055356, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 3.0 g (15 mmole) of methyl 4-(chlorocarbonyl)benzoate and 183 mg (0.2 mmole) of tris(dibenzylideneacetone)dipalladium(0) was cooled to 0° C. under N2. After 5 min, 32 mL of a 0.5 M solution of (3-cyanophenyl)(iodo)zinc in THF was added dropwise and the solution was stirred at rt. After 4 h, the reaction was quenched by addition of saturated NH4Cl solution and 30 mL ether. The layers were separated and the aqueous layer was washed with three 30 mL portions of ether. The combined organic extracts were washed with 30 mL of saturated NaHCO3 solution and 30 mL brine before being dried over MgSO4 and concentrated. The residue was dissolved in 50 mL of 1:5 CH3OH-THF and cooled to 0° C. To this was added 500 mg (13.5 mmole) of NaBH4 in two portions over 10 minutes. After 20 min, the reaction was quenched by addition of 1 mL saturated Na2SO4 solution and concentrated. The resulting slurry was diluted with ether and filtered. The solid residue was washed with ether and the combined filtrates were washed with brine, dried over Na2SO4 and concentrated to an oil that was purified by silica gel chromatography using a step-gradient of 10 to 25% EtOAc-hexane. Homogeneous fractions were combined and concentrated to afford the title compound as a white solid.

Workup

  1. waitAfter 4 h
  2. customthe reaction was quenched by addition of saturated NH4Cl solution and 30 mL ether
  3. customThe layers were separated
  4. washthe aqueous layer was washed with three 30 mL portions of ether
  5. washThe combined organic extracts were washed with 30 mL of saturated NaHCO3 solution and 30 mL brine
  6. dry with materialbefore being dried over MgSO4
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in 50 mL of 1:5 CH3OH-THF
  9. temperaturecooled to 0° C
  10. waitAfter 20 min
  11. customthe reaction was quenched by addition of 1 mL saturated Na2SO4 solution
  12. concentrationconcentrated
  13. additionThe resulting slurry was diluted with ether
  14. filtrationfiltered
  15. washThe solid residue was washed with ether
  16. washthe combined filtrates were washed with brine
  17. dry with materialdried over Na2SO4
  18. concentrationconcentrated to an oil that
  19. customwas purified by silica gel chromatography
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-dbb939d564e04866957f96501c1084f6
Source dataset
uspto-grants-2011_03
Patent number
US07906652B2

Reaction notes

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