Trimethylsilylacetylene → Benzyl 2-amino-3-ethynylbenzoate

HRID 1851407Notes

Reaction equation

HRID 1851407 reaction equation
[NH2:1][C:2]1[C:17](I)=[CH:16][CH:15]=[CH:14][C:3]=1[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5].C[Si]([C:23]#[CH:24])(C)C>C(N(CC)CC)C.C(OC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I>[NH2:1][C:2]1[C:17]([C:23]#[CH:24])=[CH:16][CH:15]=[CH:14][C:3]=1[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 57901768Benzyl 2-amino-3-iodobenzoate

Product 1

HCID 57901749Benzyl 2-amino-3-ethynylbenzoateYield 77%

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7914Diisopropyl EtherSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

A solution of benzyl 2-amino-3-iodobenzoate (5.56 g), trimethylsilylacetylene (3.26 mL), bis(triphenylphosphine)palladium(II) dichloride (0.350 g) and copper iodide (0.299 g) in triethylamine (75 mL) was stirred under a nitrogen atmosphere at room temperature for 1.5 hr. The reaction mixture was diluted with diisopropyl ether, washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (75 mL), 1.0 M tetrabutylammonium fluoride (25 mL) was added under ice-cooling, and the mixture was stirred at 0° C. for 1.5 hr. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-15:85) to give the title compound (3.06 g, yield 77%) as colorless crystals. melting point 42-43° C.

Workup

  1. washwashed successively with water and saturated brine
  2. dry with materialdried over anhydrous magnesium sulfate
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residue was dissolved in tetrahydrofuran (75 mL)
  5. addition1.0 M tetrabutylammonium fluoride (25 mL) was added under ice-
  6. temperaturecooling
  7. additionA saturated aqueous ammonium chloride solution was added to the reaction mixture
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe extract was washed successively with water and saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-15:85)

Sources & evidence

ORD record
ord-71738855fa4c4abeabcd5be6b2682b83
Source dataset
uspto-grants-2015_02
Patent number
US08957070B2

Reaction notes

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