Trimethylsilylacetylene → 3-Bromo-5-((trimethylsilyl)ethynyl)pyridine

HRID 1970952Notes

Reaction equation

HRID 1970952 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1.[CH3:9][Si:10]([C:13]#[CH:14])([CH3:12])[CH3:11]>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:8][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([C:14]#[C:13][Si:10]([CH3:12])([CH3:11])[CH3:9])[CH:7]=1

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 693693,5-Dibromopyridine

Product 1

HCID 665244243-Bromo-5-((trimethylsilyl)ethynyl)pyridine

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

To a solution of 3,5-dibromopyridine (1.0 eq, 5.0 g, 20.9 mmol) in TEA (100 ml) under an inert atmosphere of nitrogen is added copper(I) iodide (0.1 eq, 406 mg, 2.09 mmol) and PdCl2(PPh3)2 (0.1 eq, 1.5 g, 2.09 mmol). Trimethylsilylacetylene (1.2 eq, 3.6 ml, 25 mmol) is added and the resulting mixture is stirred at room temperature for 2 h. The solvent is removed in vacuo and the residue is partitioned between water and DCM. The organic portion is separated and washed with sat. aqueous NaHCO3 solution, dried (MgSO4) and concentrated in vacuo. Purification by column chromatography (hexane/DCM) yields the title compound; [M+H]+=254/256.

Workup

  1. customThe solvent is removed in vacuo
  2. customthe residue is partitioned between water and DCM
  3. customThe organic portion is separated
  4. washwashed with sat. aqueous NaHCO3 solution
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customPurification by column chromatography (hexane/DCM)

Sources & evidence

ORD record
ord-2ea010415cea409891e197c183c89677
Source dataset
uspto-grants-2013_04
Patent number
US08431578B2

Reaction notes

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