Trimethylsilylacetylene → (2-Trimethylsilanylethynylpyridin-3-yl)carbamic acid tert-butyl ester

HRID 400606Notes

Reaction equation

HRID 400606 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[C:9](Br)=[N:10][CH:11]=[CH:12][CH:13]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:16][Si:17]([C:20]#[CH:21])([CH3:19])[CH3:18]>C(N(CC)CC)C.CN(C=O)C.C(OCC)C.[Cu]I.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>[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[C:9]([C:21]#[C:20][Si:17]([CH3:19])([CH3:18])[CH3:16])=[N:10][CH:11]=[CH:12][CH:13]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 14177127(2-Bromo-Pyridin-3-Yl)-Carbamic Acid Tert-Butyl Ester

Product 1

HCID 60026792(2-Trimethylsilanylethynylpyridin-3-yl)carbamic acid tert-butyl esterYield 43%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of (2-bromopyridin-3-yl)carbamic acid tert-butyl ester (1.09 mg, 4.00 mmol), (trimethylsilyl)acetylene (2.83 mL, 20.0 mmol), CuI (75.8 mg, 0.400 mmol), and dichlorobis(triphenylphosphine)palladium (II) (141 mg, 0.200 mmol) in a mixture of 12 mL of triethylamine and 3.0 mL of anhydrous DMF were stirred at room temperature overnight. The reaction was diluted with 50 mL of diethyl ether and quenched with 50 mL of saturated aqueous ammonium chloride solution. The organic layer was washed with 20 mL of saturated aqueous ammonium chloride solution and the combined aqueous layers were extracted with three 20 mL portions of diethyl ether. The combined organic layers were then washed with 20 mL of brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. Chromatography on SiO2 (20% to 30% ethyl acetate in hexanes, gradient) gave 500 mg of (2-trimethylsilanylethynylpyridin-3-yl)carbamic acid tert-butyl ester (43% yield).

Workup

  1. customquenched with 50 mL of saturated aqueous ammonium chloride solution
  2. washThe organic layer was washed with 20 mL of saturated aqueous ammonium chloride solution
  3. extractionthe combined aqueous layers were extracted with three 20 mL portions of diethyl ether
  4. washThe combined organic layers were then washed with 20 mL of brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-fdfca58b42664c359b988642b9bb1c62
Source dataset
uspto-grants-2014_06
Patent number
US08741897B2

Reaction notes

Loading…