Triethylamine → HCID 60023923, compound

HRID 1726041Notes

Reaction equation

HRID 1726041 reaction equation
[C:1]([O:5][C:6](=[O:16])[NH:7][C@H:8]([CH:13]([CH3:15])[CH3:14])[C:9](=[O:12])[CH:10]=[CH2:11])([CH3:4])([CH3:3])[CH3:2].I[C:18]1[CH:19]=[C:20]([O:24][CH3:25])[CH:21]=[CH:22][CH:23]=1.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([O:5][C:6](=[O:16])[NH:7][C@H:8]([CH:13]([CH3:14])[CH3:15])[C:9](=[O:12])/[CH:10]=[CH:11]/[C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([O:24][CH3:25])[CH:19]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 69839Benzene, 1-iodo-3-methoxy-HCID 60023926HCID 60023926, compound

Product 1

HCID 60023923HCID 60023923, compoundYield 88.6%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of ((R)-1-Isopropyl-2-oxo-but-3-enyl)-carbamic acid tert-butyl ester (13.54 g, 59.6 mmol) in dry acetonitrile (150 mL) under argon, was added 3-iodoanisole (113.96 g, 59.6 mmol), triethylamine (9.1 mL 65.6 mmol) followed by palladium (II) acetate (335 mg, 1.49 mmol). The resulting clear yellow solution was heated to 80° C. Upon heating, the reaction darkened and the precipitation of palladium black occurred. After 15 h, the reaction mixture was allowed to cool to room temperature, quenched with water (150 mL) and diluted with ether (150 mL). The ether layer was washed with brine (100 mL) and the combined aqueous layers were extracted with ether (two 50 mL portions). The extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was immediately purified by silica gel chromatography (9:1 hexanes/EtOAc) to provide 17.6 g (88%) of [(R)-(E)-1-Isopropyl-4-(3-methoxy-phenyl)-2-oxo-but-3-enyl]-carbamic acid tert-butyl ester as a yellow oil. MS(ES+) m/e 334.0 [M+H]+.

Workup

  1. temperatureUpon heating
  2. customthe reaction darkened and the precipitation of palladium black
  3. temperatureto cool to room temperature
  4. customquenched with water (150 mL)
  5. additiondiluted with ether (150 mL)
  6. washThe ether layer was washed with brine (100 mL)
  7. extractionthe combined aqueous layers were extracted with ether (two 50 mL portions)
  8. dry with materialThe extracts were dried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was immediately purified by silica gel chromatography (9:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-295bc1c48f794f63a3c4fd45dfcf28d0
Source dataset
uspto-grants-2009_02
Patent number
US07491746B2

Reaction notes

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