4-(Trimethylsilyl)phenylboronic Acid (contains varying amounts of Anhydride) → 5-Methyl-2-(4-trimethylsilanyl-phenyl)-pyridine

HRID 2243562Notes

Reaction equation

HRID 2243562 reaction equation
[CH3:1][Si:2]([CH3:13])([CH3:12])[C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][N:16]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C(P(C(C)(C)C)C(C)(C)C)C1C=CC=CC=1>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.O1CCOCC1>[CH3:21][C:18]1[CH:19]=[CH:20][C:15]([C:6]2[CH:7]=[CH:8][C:3]([Si:2]([CH3:13])([CH3:12])[CH3:1])=[CH:4][CH:5]=2)=[N:16][CH:17]=1

Participants

7

Reactant 4

HCID 17104-(Trimethylsilyl)phenylboronic Acid (contains varying amounts of Anhydride)HCID 10796Cesium carbonateHCID 5642162-Bromo-5-methylpyridineHCID 11170394Benzyl-di-t-butylphosphine

Product 1

HCID 252596005-Methyl-2-(4-trimethylsilanyl-phenyl)-pyridine

Reagents, catalysts & solvents 2

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

15.0 g (0.0773 mol) of 4-trimethylsilyl-phenylboronic acid, 11.96 g (0.0695 mol) of 2-bromo-5-methyl-pyridine, 15.11 g (0.0464 mol) of cesium carbonate, 0.71 g (0.000776 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.43 g (0.00182 mol) of benzyl-di-tert-butyl-phosphane and 100 ml of dioxane were stirred at room temperature for 12 hr. The reaction mixture was filtered and the solvent was removed under 1 mm vacuum. The resulting mixture was purified by distillation in vacuum. Yield of 5-methyl-2-(4-trimethylsilanyl-phenyl)-pyridine was 8.05 g (48%) as a yellow solid with b.p. 111-114° C./0.02 mm and m.p. 66.07° C. 1H NMR (CD2Cl2) 2.15 (s, 3H, Me) 7.45-8.50 (m, 7H, arom-H). Anal. Found: C, 74.34; H, 7.86; N, 5.85. The structure was confirmed by X-ray analysis.

Workup

  1. filtrationThe reaction mixture was filtered
  2. customthe solvent was removed under 1 mm vacuum
  3. distillationThe resulting mixture was purified by distillation in vacuum

Sources & evidence

ORD record
ord-4f1e001641424537991408d7b20f3b17
Source dataset
uspto-grants-2010_03
Patent number
US07675228B2

Reaction notes

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