Trimethylsilylacetylene → (4-Tert-butyl-benzyl)-[2-(3-trimethylsilanylethynyl-phenyl)-ethyl]-carbamic acid tert-butyl ester

HRID 19795Notes

Reaction equation

HRID 19795 reaction equation
[C:1]([O:5][C:6](=[O:28])[N:7]([CH2:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23](Br)[CH:22]=1)[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:11][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:29][Si:30]([C:33]#[CH:34])([CH3:32])[CH3:31]>C(N(CC)CC)C.C([O-])(O)=O.[Na+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[C:1]([O:5][C:6](=[O:28])[N:7]([CH2:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:11][CH:10]=1)[CH2:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([C:34]#[C:33][Si:30]([CH3:32])([CH3:31])[CH3:29])[CH:22]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 68562789HCID 68562789, compound

Product 1

HCID 68560300(4-Tert-butyl-benzyl)-[2-(3-trimethylsilanylethynyl-phenyl)-ethyl]-carbamic acid tert-butyl esterYield 82.4%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
105 °C

Procedure

A mixture of the crude [2-(3-bromo-phenyl)-ethyl]-(4-tert-butyl-benzyl)-carbamic acid tert-butyl ester (515 mg, 1.154 mmol), bis(triphenylphosphine)palladium(II)chloride (32 mg, 0.0461 mmol), CuI (11 mg, 0.0577 mmol) and (trimethylsilyl)acetylene (251 μl, 1.73 mmol) in triethylamine (3.4 ml) was heated in a sealed tube at 105° C. over night. The mixture was then cooled to RT, diluted with sat. NaHCO3-solution and extracted three times with ethyl acetate. The combined ethyl acetate layers were then washed with water and brine and were dried (Na2SO4) and evaporated. The remaining residue was purified by chromatography (heptane/EtOAc 100:0 to 95:5) to obtain the title compound as a yellow gum (441 mg, 82%). MS (ISP) 464.4 (M+H)+.

Workup

  1. temperatureThe mixture was then cooled to RT
  2. extractionextracted three times with ethyl acetate
  3. washThe combined ethyl acetate layers were then washed with water and brine
  4. dry with materialwere dried (Na2SO4)
  5. customevaporated
  6. customThe remaining residue was purified by chromatography (heptane/EtOAc 100:0 to 95:5)

Sources & evidence

ORD record
ord-8c4a07f24aa3494b88f1f616f709d796
Source dataset
uspto-grants-2010_06
Patent number
US07745477B2

Reaction notes

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