Triethylamine → HCID 57486350, compound

HRID 597986Notes

Reaction equation

HRID 597986 reaction equation
FC(F)(F)S(O[C:7]1[CH:13]2[CH2:14][CH:10]([CH2:11][N:12]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:9][CH:8]=1)(=O)=O.C(N(CC)CC)C.[CH3:31][Si:32]([C:35]#[CH:36])([CH3:34])[CH3:33]>C1(C)C=CC=CC=1>[CH3:31][Si:32]([C:35]#[C:36][C:7]1[CH:13]2[CH2:14][CH:10]([CH2:11][N:12]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:9][CH:8]=1)([CH3:34])[CH3:33]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 57486345HCID 57486345, compound

Product 1

HCID 57486350HCID 57486350, compoundYield 58.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of t-butyl 4-trifluoromethanesulfonyloxy-6-azabicyclo[3.2.1]oct-3-ene-6-carboxylate (1.8 g, 5.0 mmol) in 10 mL of toluene was added 20 mL of triethylamine, followed by trimethylsilylacetylene (0.49 g, 5.0 mmol). The mixture was degassed, placed under a nitrogen atmosphere, and copper iodide (50 mg) and bis(triphenylphosphine)palladium dichloride (100 mg) were added. The reaction mixture was heated under reflux for 16 h, then cooled and concentrated under reduced pressure. The residue was chromatographed on a silica gel column, using 0-50% ethyl acetate in hexane as eluent, to give tert-butyl 4-trimethylsilylethynyl-6-azabicyclo[3.2.1]oct-3-ene-6-carboxylate (900 mg, 58.9%). This was dissolved in 25 mL of methanol and treated with solid potassium carbonate (˜1 g) with vigorous stirring. After 4 h, the mixture was concentrated to dryness in vacuo, and the residue was column chromatographed on silica gel, eluting with 2:1 hexane/ethyl acetate, to give a yellow oil (300 mg, 25.8% for two steps).

Workup

  1. customThe mixture was degassed
  2. additioncopper iodide (50 mg) and bis(triphenylphosphine)palladium dichloride (100 mg) were added
  3. temperatureThe reaction mixture was heated
  4. temperatureunder reflux for 16 h
  5. temperaturecooled
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was chromatographed on a silica gel column

Sources & evidence

ORD record
ord-8e7bac8443b94751b1e8bc28fbcc03f1
Source dataset
uspto-grants-2011_03
Patent number
US07897611B2

Reaction notes

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