tert-Butyl acrylate → (E)-tert-Butyl 3-(6-acetyl-3-chloro-2-fluorophenyl)acrylate

HRID 1054129Notes

Reaction equation

HRID 1054129 reaction equation
Br[C:2]1[C:7]([F:8])=[C:6]([Cl:9])[CH:5]=[CH:4][C:3]=1[C:10](=[O:12])[CH3:11].[C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])(=[O:16])[CH:14]=[CH2:15]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:10]([C:3]1[C:2](/[CH:15]=[CH:14]/[C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[C:7]([F:8])[C:6]([Cl:9])=[CH:5][CH:4]=1)(=[O:12])[CH3:11]

Participants

5

Reactant 2

HCID 15458tert-Butyl acrylateHCID 666985481-(2-Bromo-4-chloro-3-fluorophenyl)ethanone

Product 1

HCID 66698573(E)-tert-Butyl 3-(6-acetyl-3-chloro-2-fluorophenyl)acrylateYield 50.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of Intermediate 12C (50 g, 198 mmol), tert-butyl acrylate (50.9 g, 397 mmol) and TEA (55 mL, 397 mmol) in DMF (500 mL) was added Pd(OAc)2 (8.9 g, 39.7 mmol). The resulting mixture was stirred at 90° C. overnight. The reaction was cooled to rt, filtered, and the filtrate was concentrated. Purification by column chromatography gave Intermediate 12D (30 g, 50.8%) as a light yellow solid. MS (ESI) m/z: 242.7 (M+H)+.

Workup

  1. temperatureThe reaction was cooled to rt
  2. filtrationfiltered
  3. concentrationthe filtrate was concentrated
  4. customPurification by column chromatography

Sources & evidence

ORD record
ord-848486e9a86b4faba0959d8aec8739dc
Source dataset
uspto-grants-2016_07
Patent number
US09394276B2

Reaction notes

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