3,5-Dibromopyridine → HCID 18187614, compound

HRID 2367666Notes

Reaction equation

HRID 2367666 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1.[Br-].[CH2:10]([Zn+])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C1COCC1.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:10]([C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

6

Reactant 2

HCID 693693,5-DibromopyridineHCID 178419772HCID 178419772, compound

Product 1

HCID 18187614HCID 18187614, compoundYield 57%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 3,5-dibromopyridine (XXXIV) (1.03 g, 4.36 mmol) in THF (7 mL) under argon was added CuI (50 mg, 0.26 mmol) and PdCl2(dppf)2 (178 mg, 0.22 mmol). Benzylzinc(II) bromide (XXXV) (0.5M in THF) (13.09 mL, 6.55 mmol) was slowly added by syringe. The reaction was heated at 50° C. over the weekend. The reaction was quenched with water and extracted with EtOAc. The EtOAc was separated, washed with water, brine, dried over MgSO4 and concentrated under vacuum. The residue was purified on a silica gel column (100% hexanes→5:95 EtOAc:hexanes) to afford 3-benzyl-5-bromopyridine (XXXVI) (0.614 g, 2.47 mmol, 57% yield) as a light brown oil. 1H NMR (DMSO-d6) δ ppm 3.98 (s, 2H), 7.19-7.23 (m, 1H), 7.27-7.32 (m, 4H), 7.92-7.93 (m, 1H), 8.51 (d, J=2 Hz, 1H), 8.54 (d, J=3 Hz, 1H); ESIMS found for C12H10BrN m/z 248 (M+H).

Workup

  1. customThe reaction was quenched with water
  2. extractionextracted with EtOAc
  3. customThe EtOAc was separated
  4. washwashed with water, brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified on a silica gel column (100% hexanes→5:95 EtOAc:hexanes)

Sources & evidence

ORD record
ord-ae060db6224245849b2a108d570cb14f
Source dataset
uspto-grants-2014_04
Patent number
US08697887B2

Reaction notes

Loading…