Ethyl 4-iodobenzoate → Ethyl 4-[(2,2-dimethyl-4-oxo-chroman-6-yl)ethynyl]-benzoate

HRID 619649Notes

Reaction equation

HRID 619649 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[O:9][C:8]([CH3:14])([CH3:13])[CH2:7][C:6]2=[O:15])#[CH:2].I[C:17]1[CH:27]=[CH:26][C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:19][CH:18]=1>CCN(CC)CC.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>[CH3:14][C:8]1([CH3:13])[CH2:7][C:6](=[O:15])[C:5]2[C:10](=[CH:11][CH:12]=[C:3]([C:1]#[C:2][C:17]3[CH:27]=[CH:26][C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:19][CH:18]=3)[CH:4]=2)[O:9]1

Participants

6

Reactant 2

HCID 142891Ethyl 4-iodobenzoateHCID 218466816-Ethynyl-2,2-dimethylchroman-4-one2×

Product 1

HCID 21846646Ethyl 4-[(2,2-dimethyl-4-oxo-chroman-6-yl)ethynyl]-benzoateYield 50.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A solution of 6-ethynyl-2,2-dimethylchroman-4-one (Compound 262, 2.60 g, 13.0 mmol) and ethyl 4-iodobenzoate (3.6 g, 13.0 mmol) in 50.0 mL Et3N was purged with argon for 15 minutes. To this solution was added bis(triphenylphosphine)-palladium(II) chloride (1.82 g, 2.6 mmol) and copper(I) iodide (496 mg, 2.6 mmol). After sparging for an additional 10 minutes with argon, the solution was stirred overnight at room temperature. The reaction mixture was filtered through a pad of Celite using an Et2O wash. Concentration of the filtrate under reduced pressure, followed by column chromatography (2-5% EtOAc-hexanes) of the residual solid afforded 2.28 g (50%) the title compound as an orange solid. 1H NMR (300 MHz, CDCl3) δ: 8.06 (1H, d, J=2.2 Hz), 8.02 (2H, d, J=8.5 Hz), 2.61 (1H, dd, J=2.2, 8.6 Hz), 7.55 (2H, d, J=8.5 Hz), 6.93 (1H, d, J=8.6 Hz), 4.39 (2H, q, J=7.1 Hz), 2.75 (3H, s), 1.48 (6H, s), 1.41 (t, J=7.1 Hz).

Workup

  1. customAfter sparging for an additional 10 minutes with argon
  2. filtrationThe reaction mixture was filtered through a pad of Celite
  3. washwash

Sources & evidence

ORD record
ord-ee19218a55e14a52a9edeb3e485bc7c7
Source dataset
uspto-grants-1999_09
Patent number
US05958954

Reaction notes

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