Cesium fluoride → Rac-2-(4-ethynyl-2,6-dimethylphenyl)-3-methoxy-5-pyridin-2-ylmethylcyclopent-2-enone

HRID 514198Notes

Reaction equation

HRID 514198 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]2[C:10](=[O:23])[CH:11]([CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)[CH2:12][C:13]=2[O:14][CH3:15])=[C:4]([CH3:24])[CH:3]=1.[F-].[Cs+].[C:27]([Sn](CCCC)(CCCC)CCCC)#[CH:28]>CN(C)C=O.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[C:27]([C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]2[C:10](=[O:23])[CH:11]([CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)[CH2:12][C:13]=2[O:14][CH3:15])=[C:4]([CH3:24])[CH:3]=1)#[CH:28]

Participants

7

Reactant 3

HCID 25953Cesium fluorideHCID 621176EthynyltributyltinHCID 89600800Rac-2-(4-bromo-2,6-dimethylphenyl)-3-methoxy-5-pyridin-2-ylmethylcyclopent-2-enone

Product 1

HCID 89601448Rac-2-(4-ethynyl-2,6-dimethylphenyl)-3-methoxy-5-pyridin-2-ylmethylcyclopent-2-enone

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

To a mixture of rac-2-(4-bromo-2,6-dimethylphenyl)-3-methoxy-5-pyridin-2-ylmethylcyclopent-2-enone (0.50 g, 1.29 mmol), cesium fluoride (0.39 g, 2.59 mmol) and copper(I) iodide (0.025 g, 0.129 mmol) in N,N-dimethylformamide (5.0 ml) is added [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.053 g, 0.065 mmol) and ethynyltributylstannane (1.22 g, 3.88 mmol). The reaction mixture is heated at 110°C. under microwave irradiation for 60 mins, then allowed to cool to room temperature and is quenched with distilled water (20 ml) and extracted with ethyl acetate. The combined organic fractions are dried over magnesium sulfate, filtered and the filtrate evaporated in vacuo. The crude product is purified by flash column chromatography (0-8% methanol in dichloromethane as eluant) to afford rac-2-(4-ethynyl-2,6-dimethylphenyl)-3-methoxy-5-pyridin-2-ylmethylcyclopent-2-enone.

Workup

  1. temperatureto cool to room temperature
  2. customis quenched with distilled water (20 ml)
  3. extractionextracted with ethyl acetate
  4. dry with materialThe combined organic fractions are dried over magnesium sulfate
  5. filtrationfiltered
  6. customthe filtrate evaporated in vacuo
  7. customThe crude product is purified by flash column chromatography (0-8% methanol in dichloromethane as eluant)

Sources & evidence

ORD record
ord-50f4135968d2425fbc74fed4f10ef889
Source dataset
uspto-grants-2015_08
Patent number
US09107415B2

Reaction notes

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