2-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenyl → Tert-butyl 2-(2-chloro-4-cyanophenyl)acetate

HRID 578932Notes

Reaction equation

HRID 578932 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[Cl:10].[Cl-].[C:12]([O:16][C:17](=[O:20])[CH2:18][Zn+])([CH3:15])([CH3:14])[CH3:13].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(N(C)C)=CC=CC=2)CCCCC1>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[Cl:10][C:3]1[CH:4]=[C:5]([C:6]#[N:7])[CH:8]=[CH:9][C:2]=1[CH2:18][C:17]([O:16][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:20]

Participants

6

Reactant 3

HCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 166593954-Bromo-3-chlorobenzonitrileHCID 178451183HCID 178451183, compound

Product 1

HCID 117601114Tert-butyl 2-(2-chloro-4-cyanophenyl)acetateYield 39.3%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

Combined 4-bromo-3-chlorobenzonitrile (0.600 g, 2.77 mmol) and (2-(tert-butoxy)-2-oxoethyl)zinc(II) chloride (8.32 mL, 4.16 mmol) in THF (5.54 mL), then Pd(dba)2 (0.080 g, 0.139 mmol) and 2′-(dicyclohexylphosphino)-N,N-dimethyl-[1,1′-biphenyl]-2-amine (0.109 g, 0.277 mmol) were added and the reaction was refluxed overnight at 65° C. The reaction was concentrated by rotary evaporation and purified on a silica gel column eluting with hexanes and EtOAc to give the title compound (274 mg, 39%) as a yellow oil. MS m/z [M+H]+ 252.

Workup

  1. concentrationThe reaction was concentrated by rotary evaporation
  2. custompurified on a silica gel column
  3. washeluting with hexanes and EtOAc

Sources & evidence

ORD record
ord-3ddb4e1116d64bc693f83b7071a60602
Source dataset
uspto-grants-2015_05
Patent number
US09040522B2

Reaction notes

Loading…