Cesium carbonate → (4'-Chloro-3,5-diethylbiphen-4-yl)carbamic acid tert-butyl ester

HRID 72282Notes

Reaction equation

HRID 72282 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].[C:7]([O:11][C:12](=[O:25])[NH:13][C:14]1[C:19]([CH2:20][CH3:21])=[CH:18][C:17](Br)=[CH:16][C:15]=1[CH2:23][CH3:24])([CH3:10])([CH3:9])[CH3:8].[Cl:26][C:27]1[CH:32]=[CH:31][C:30](B(O)O)=[CH:29][CH:28]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>O.CC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:7]([O:11][C:12](=[O:25])[NH:13][C:14]1[C:19]([CH2:20][CH3:21])=[CH:18][C:17]([C:30]2[CH:31]=[CH:32][C:27]([Cl:26])=[CH:28][CH:29]=2)=[CH:16][C:15]=1[CH2:23][CH3:24])([CH3:10])([CH3:9])[CH3:8]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 742994-Chlorophenylboronic acidHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 59450511tert-Butyl (4-bromo-2,6-diethylphenyl)carbamate

Product 1

HCID 59450514(4'-Chloro-3,5-diethylbiphen-4-yl)carbamic acid tert-butyl esterYield 67.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

A solution of cesium carbonate (89.12 g, 0.27 mol) in water (600 ml) is added to a degassed solution of (4-bromo-2,6-diethylphenyl)carbamic acid tert-butyl ester (30 g, 0.091 mol) and 4-chlorophenylboronic acid (21.54 g, 0.138 mol) in acetone (3 L), and the mixture is stirred at room temperature under an atmosphere of nitrogen. Palladium acetate (1.02 g, 0.004 mol) and 2-(dicyclohexylphosphino)-2′,4′,6′-tri-iso-propyl-1,1′-biphenyl (4.33 g, 0.009 mol) are added and the reaction mixture is stirred at room temperature for 12 hours. The mixture is filtered through diatomaceous earth, and the filtrate is evaporated under reduced pressure to remove most of the acetone. The remaining solution is extracted with ethyl acetate (3×300 ml). The organic extracts are combined and concentrated under reduced pressure to give (4′-chloro-3,5-diethylbiphen-4-yl)carbamic acid tert-butyl ester (22 g).

Workup

  1. stirringthe reaction mixture is stirred at room temperature for 12 hours
  2. filtrationThe mixture is filtered through diatomaceous earth
  3. customthe filtrate is evaporated under reduced pressure
  4. customto remove most of the acetone
  5. extractionThe remaining solution is extracted with ethyl acetate (3×300 ml)
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-801fd93d49f948198bd40fba334e2bc0
Source dataset
uspto-grants-2014_09
Patent number
US08828908B2

Reaction notes

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