Acetonitrile → HCID 86621470, compound

HRID 2241021Notes

Reaction equation

HRID 2241021 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:15]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[C:22]([O:26][C:27](=[O:30])[CH:28]=[CH2:29])([CH3:25])([CH3:24])[CH3:23].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CC#N>CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:15]1(=[C:8]([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:5]2[CH:6]=[CH:7][C:2](/[CH:29]=[CH:28]/[C:27]([O:26][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:30])=[CH:3][CH:4]=2)[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]1

Participants

8

Reactant 4

HCID 6342AcetonitrileHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 68505673HCID 68505673, compound

Product 1

HCID 86621470HCID 86621470, compoundYield 103.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A stirred suspension of 1 (0.77 g, 2.24 mmol), TEA (1.86 mL, 13.4 mmol), t-butylacrylate (1.96 mL, 13.4 mmol), Pd(OAc)2 (0.12 g, 0.50 mmol), P(o-tolyl)3 (0.28 g, 0.90 mmol) and CH3CN were stirred at reflux under N2. Heating was discontinued after 2 h and the reaction diluted with EtOAc (50 mL) and water (50 mL). The mixture was filtered through a celite pad and the filtrate transferred to a separatory funnel. The organic fraction was washed with 50 mL brine (50 mL), dried (MgSO4), filtered and concentrated to 1.39 g of an amber oil. The crude product was purified by flash chromatography on silica gel with a hexanes to 5% EtOAc:hexanes gradient. The product, 2, was isolated as a colorless, viscous oil (900 mg, 100%). 1H NMR (300 MHz, DMSO-d6): δ 1.52 (s, 9H), 1.59 (s, 8H), 2.31 (br, 4H), 6.51 (d, J=16 Hz, 1H), 7.19-7.38 (m, 7H), 7.56 (d, J=16 Hz, 1H), 7.66 (d, J=8.1 Hz, 2H).

Workup

  1. temperatureat reflux under N2
  2. temperatureHeating
  3. filtrationThe mixture was filtered through a celite pad
  4. customthe filtrate transferred to a separatory funnel
  5. washThe organic fraction was washed with 50 mL brine (50 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated to 1.39 g of an amber oil
  9. customThe crude product was purified by flash chromatography on silica gel with a hexanes to 5% EtOAc

Sources & evidence

ORD record
ord-47826f1b836e449c9dd1d8668099a901
Source dataset
uspto-grants-2010_05
Patent number
US07723393B2

Reaction notes

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