3-Bromo-1-(trimethylsilyl)-1-propyne → 3-(4-(Trimethylsilyl)-1-(pyridin-3-yl)but-3-ynyl)pyridine

HRID 1686081Notes

Reaction equation

HRID 1686081 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:2]=1.[Li+].CC([N-]C(C)C)C.Br[CH2:23][C:24]#[C:25][Si:26]([CH3:29])([CH3:28])[CH3:27]>C1COCC1>[CH3:27][Si:26]([CH3:29])([CH3:28])[C:25]#[C:24][CH2:23][CH:7]([C:8]1[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=1)[C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 6425893-Bromo-1-(trimethylsilyl)-1-propyneHCID 2724682Lithium diisopropylamideHCID 147626403,3'-Methylenedipyridine

Product 1

HCID 672647103-(4-(Trimethylsilyl)-1-(pyridin-3-yl)but-3-ynyl)pyridine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In an oven-dried 100-mL round-bottom flask was placed di(pyridin-3-yl)methane (0.100 g, 0.58 mmol) in dry THF (10 mL) under N2. The solution was cooled to 0° C. and LDA (0.580 mL of a 1.5 M solution, 0.87 mmol) was slowly added to form a dark red suspension. The suspension was stirred for 15 min at 0° C. and then 3-bromo-1-(trimethylsilyl)-1-propyne (0.164 mL, 1.16 mmol) was added via syringe. The reaction was warmed to rt, quenched with water (1 mL), and extracted with dichloromethane (2×25 mL). The organic layers were combined and dried over Na2SO4, filtered and concentrated to give the crude product 3-(4-(trimethylsilyl)-1-(pyridin-3-yl)but-3-ynyl)pyridine. This material was dissolved in methanol (5 mL), K2CO3 (0.500 g, 3.6 mmol) was added, and the mixture was stirred at rt for 48 h. The reaction was filtered and washed with dichloromethane (2×10 mL), then concentrated and dried. Purification by reverse phase chromatography gave 0.119 g (47%) of 3-(1-(pyridin-3-yl)but-3-ynyl)pyridine as a TFA salt. Analytical LCMS: single peak (214 nm), 0.416 min. ESIMS m/z 209.1 (C14H12N2+H+ requires 209.1079).

Workup

  1. customIn an oven-dried 100-mL round-bottom flask was placed
  2. customto form a dark red suspension
  3. temperatureThe reaction was warmed to rt
  4. customquenched with water (1 mL)
  5. extractionextracted with dichloromethane (2×25 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-280618707edc40dea86e53ee087db61b
Source dataset
uspto-grants-2012_04
Patent number
US08148535B2

Reaction notes

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