Pivaloyl chloride → Ethyl 2,2,7,7-tetramethyl-6-oxooct-4-ynoate

HRID 1917596Notes

Reaction equation

HRID 1917596 reaction equation
[CH3:1][C:2]([CH3:11])([CH2:8][C:9]#[CH:10])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH3:12][C:13]([CH3:18])([CH3:17])[C:14](Cl)=[O:15]>C(N(CC)CC)C.[Cu]I>[CH3:11][C:2]([CH3:1])([CH2:8][C:9]#[C:10][C:14](=[O:15])[C:13]([CH3:18])([CH3:17])[CH3:12])[C:3]([O:5][CH2:6][CH3:7])=[O:4]

Participants

5

Reactant 2

HCID 62493Pivaloyl chlorideHCID 14459632Ethyl 2,2-dimethylpent-4-ynoate

Product 1

HCID 58505758Ethyl 2,2,7,7-tetramethyl-6-oxooct-4-ynoateYield 54%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
23 °C

Procedure

To a solution of ethyl 2,2-dimethylpent-4-ynoate (1.00 g, 6.5 mmol), 2,2-dimethyl-propionyl chloride (0.8 mL, 6.5 mmol), and dichlorobis(triphenylphosphine) palladium(II) (460 mg, 0.65 mmol) in triethylamine (TEA) (12 mL) is added CuI (62 mg, 0.32 mmol). The mixture is stirred at 23° C. for 3 h then partitioned between Et2O and saturated aqueous NH4Cl. The organics are washed with water, dried with MgSO4, filtered, and concentrated in vacuo. The residue is purified by flash chromatography (SiO2, hexanes to 10% EtOAc in hexanes) to give the title intermediate (828 mg, 54%).

Workup

  1. customthen partitioned between Et2O and saturated aqueous NH4Cl
  2. washThe organics are washed with water
  3. dry with materialdried with MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue is purified by flash chromatography (SiO2, hexanes to 10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-aee81fe8b83f4ef4828c1e247b05dcf9
Source dataset
uspto-grants-2013_12
Patent number
US08618300B2

Reaction notes

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