Methanol → 2-[(Tert-butyldimethylsilanyl)ethynyl]-5-(4-chlorophenyl)pyridine

HRID 734778Notes

Reaction equation

HRID 734778 reaction equation
CO.C(=O)([O-])[O-].[Na+].[Na+].Br[C:10]1[CH:11]=[CH:12][C:13]([C:16]#[C:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])=[N:14][CH:15]=1.[Cl:25][C:26]1[CH:31]=[CH:30][C:29](OB(O)O)=[CH:28][CH:27]=1>O1CCOCC1.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]>[Si:18]([C:17]#[C:16][C:13]1[CH:12]=[CH:11][C:10]([C:29]2[CH:30]=[CH:31][C:26]([Cl:25])=[CH:27][CH:28]=2)=[CH:15][N:14]=1)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 887MethanolHCID 10340Sodium CarbonateHCID 17810664p-Chlorophenylboric acidHCID 666112135-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

Product 1

HCID 690583502-[(Tert-butyldimethylsilanyl)ethynyl]-5-(4-chlorophenyl)pyridine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Procedure

250 mL of MeOH, 220 mL of 2N sodium carbonate solution, and 1.80 g (2.46 mmol) of PdCl2(dppf) were added to a solution of 59.5 g (201.0 mmol) of 5-bromo-2-[(tert-butyldimethylsilanyl)ethynyl]pyridine and 36.5 g (233.4 mmol) of 4-chlorophenylboric acid in 600 mL of 1,4-dioxane and the mixture was refluxed for 1 hour. The reaction mixture was evaporated down in vacuo and diluted with EtOAc. The organic phase was washed with water and semisaturated sodium bicarbonate solution, dried over sodium sulfate and evaporated down in vacuo. The residue was purified by column chromatography (silica gel, cyc/EtOAc 9:1). Yield: 38.5 g (58% of theoretical); C19H22ClNSi (M=327.923); calc.: molpeak (M+H)+: 328/330 (Cl); found: molpeak (M+H)+: 328/330 (Cl); Rf value: 0.60 (silica gel, cyc/EtOAc 8:1).

Workup

  1. temperaturethe mixture was refluxed for 1 hour
  2. customThe reaction mixture was evaporated down in vacuo
  3. additiondiluted with EtOAc
  4. washThe organic phase was washed with water and semisaturated sodium bicarbonate solution
  5. dry with materialdried over sodium sulfate
  6. customevaporated down in vacuo
  7. customThe residue was purified by column chromatography (silica gel, cyc/EtOAc 9:1)

Sources & evidence

ORD record
ord-188db54c07644c41b6def27a1c3c08ae
Source dataset
uspto-grants-2009_09
Patent number
US07592358B2

Reaction notes

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