3-Bromobenzonitrile → Tert-butyl 2-(3-cyanophenyl)acetate

HRID 526406Notes

Reaction equation

HRID 526406 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[C:5]#[N:6].[Cl-].[C:11]([O:15][C:16](=[O:19])[CH2:17][Zn+])([CH3:14])([CH3:13])[CH3:12].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]>[C:5]([C:4]1[CH:3]=[C:2]([CH2:17][C:16]([O:15][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:19])[CH:9]=[CH:8][CH:7]=1)#[N:6]

Participants

6

Reactant 3

HCID 233813-BromobenzonitrileHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 178451183HCID 178451183, compound

Product 1

HCID 102224183Tert-butyl 2-(3-cyanophenyl)acetateYield 86%

Reagents, catalysts & solvents 2

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

Procedure

Combined 3-bromobenzonitrile (1500 mg, 8.24 mmol), 0.5 M (2-(tert-butoxy)-2-oxoethyl)zinc(II) chloride (24.72 mL, 12.36 mmol), 2′-(dicyclohexylphosphino)-N,N-dimethyl-[1,1′-biphenyl]-2-amine (324 mg, 0.824 mmol) and Pd(dba)2 (237 mg, 0.412 mmol) in THF (25 mL) and heated at 100° in an oil bath for 14 h. The reaction solution was concentrated onto Celite® and chromatographed on a 120 g silica gel column eluted with 0 to 50% EtOAc in hexanes to give the title compound (1.537 g, 86% yield) as a yellow oil. MS m/z 218 [M+H]+. 1H NMR (400 MHz, chloroform-d) δ ppm 1.45 (s, 9H) 3.56 (s, 2H) 7.40-7.46 (m, 1H) 7.49-7.54 (m, 1H) 7.54-7.59 (m, 2H).

Workup

  1. concentrationThe reaction solution was concentrated onto Celite®
  2. customchromatographed on a 120 g silica gel column
  3. washeluted with 0 to 50% EtOAc in hexanes

Sources & evidence

ORD record
ord-418b488ea34c4fec844b8fbb546bcf61
Source dataset
uspto-grants-2016_05
Patent number
US09345713B2

Reaction notes

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