Tributylamine → (E)-tert-butyl 3-(2-acetyl-5-chlorophenyl)acrylate

HRID 716624Notes

Reaction equation

Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:11])[CH3:10].C(N(CCCC)CCCC)CCC.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27]>CN(C=O)C.[Pd].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:9]([C:3]1[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=1/[CH:27]=[CH:26]/[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])(=[O:11])[CH3:10]

Participants

Conditions

Temperature: 100 °C

Procedure

To a degassed solution of 1-(2-bromo-4-chlorophenyl)ethanone (1.0 g, 4.28 mmol), tributylamine (2.041 mL, 8.57 mmol), and tert-butyl acrylate (1.255 mL, 8.57 mmol) in DMF (10 mL) was added palladium on carbon (0.456 g, 0.428 mmol) and palladium (II) acetate (0.096 g, 0.428 mmol). The reaction mixture was warmed to 100° C. After 16 h, the reaction was cooled to rt and filtered. The solid was rinsed with DMF and the filtrate was diluted with EtOAc and washed with H2O (2×) followed by brine. The crude product was then dried over Na2SO4, filtered and concentrated. Purification by normal phase chromatography afforded Intermediate 4A (0.760 g, 63%), as a brown oil. MS (ESI) m/z: 225.0 (M-C4H8+H)+.

Workup

temperaturethe reaction was cooled to rt
filtrationfiltered
washThe solid was rinsed with DMF
additionthe filtrate was diluted with EtOAc
washwashed with H2O (2×)
dry with materialThe crude product was then dried over Na2SO4
filtrationfiltered
concentrationconcentrated
customPurification by normal phase chromatography

Sources & evidence

ORD record: ord-1286c98855634433b5c8c3ae352372a5
Source dataset: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09192607B2

Reaction notes

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