Methanol → 2-((tert-Butyldimethylsilyl)ethynyl)-5-p-tolylpyridine

HRID 76139Notes

Reaction equation

HRID 76139 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]#[C:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])=[N:6][CH:7]=1.CO.[C:19]1([CH3:28])[CH:24]=[CH:23][C:22](B(O)O)=[CH:21][CH:20]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1>[Si:10]([C:9]#[C:8][C:5]1[CH:4]=[CH:3][C:2]([C:22]2[CH:23]=[CH:24][C:19]([CH3:28])=[CH:20][CH:21]=2)=[CH:7][N:6]=1)([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11]

Participants

6

Reactant 4

HCID 887MethanolHCID 10340Sodium CarbonateHCID 79799Tolylboronic acidHCID 666112135-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

Product 1

HCID 666115662-((tert-Butyldimethylsilyl)ethynyl)-5-p-tolylpyridine

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

4.6 g (15.00 mmol) 5-bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine are added to 12 mL methanol and 50 mL 1,4-dioxane. Then the mixture is charged with 2.40 g (17.3 mmol) p-tolyl-boronic acid, 0.1 g (0.15 mmol) bis(triphenyphosphine)-dichloropalladium and 16.5 mL (33.0 mmol) of a 2N aq. Na2CO3 solution. The reaction mixture is stirred at reflux for 2 h. Then the solvent is removed in vacuo to some extent and the residue is diluted with EtOAc and water. The organic layer is sequently washed with 50 mL half sat. Na2CO3 solution (1×) and 50 mL water (1×). The organic layer is dried with MgSO4 and the solvent is removed in vacuo. The residue is treated with DIPE and PE to receive a precipitate which is filtered and dried to yield the desired product.

Workup

  1. temperatureat reflux for 2 h
  2. customThen the solvent is removed in vacuo to some extent
  3. additionthe residue is diluted with EtOAc and water
  4. washThe organic layer is sequently washed with 50 mL half sat. Na2CO3 solution (1×) and 50 mL water (1×)
  5. dry with materialThe organic layer is dried with MgSO4
  6. customthe solvent is removed in vacuo
  7. additionThe residue is treated with DIPE and PE
  8. filtrationis filtered
  9. customdried

Sources & evidence

ORD record
ord-061cf6bf79f24d2f9e478810844d539b
Source dataset
uspto-grants-2014_09
Patent number
US08835472B2

Reaction notes

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