Dimethylformamide → HCID 137329844, compound

HRID 2228405Notes

Reaction equation

HRID 2228405 reaction equation
[CH2:1]([C:4]1[CH:5]=[C:6]([SiH:11]([CH3:13])[CH3:12])[C:7](Br)=[N:8][CH:9]=1)[CH:2]=[CH2:3].C([Li])CCC.CN([CH:22]=[O:23])C>C1COCC1>[CH2:1]([C:4]1[CH:5]=[C:6]([SiH:11]([CH3:13])[CH3:12])[C:7]([CH:22]=[O:23])=[N:8][CH:9]=1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 137329843HCID 137329843, compoundHCID 178418339Butyllithium

Product 1

HCID 137329844HCID 137329844, compoundYield 36.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 5-allyldimethylsilyl-2-bromopyridine (7 Scheme 27, 14.5 g, 56 mmol) in dry THF (400 mL) at −78° C. was added n-butyllithium (2.5 M in hexanes, 22.5 mL, 56 mmol) over a period of 20 min. After stirring 30 min at this temperature, anhydrous DMF (6.5 mL, 84 mmol) was added over a period of 5 min, and the reaction mixture was stirred for 30 min then warmed to room temperature. Saturated NCl (10 mL) was added to the reaction mixture. The layers were separated, and the organic layer was dried (Na2SO4), concentrated. The crude product was purified by column chromatography (1:7 ethyl acetate/hexanes) to afford an oil (4.2 g, 36%); 1H NMR (300 MHz, CDCl3) δ 0.26 (s, 6 H), 1.71 (d, J=8.40 Hz, 2 H), 4.74 (m, 1 H), 4.79 (s, 1 H), 5.62 (m, 1 H), 7.80 (d, J=7.80 Hz, 1 H), 7.89 (m, 1 H), 8.75 (d, J=0.90 Hz, 1 h), 9.97 (s, 1 H); 13C NMR (75 MHz, CDCl3) 3.65 (2C), 23.1, 114.7, 120.7, 133.3, 139.9, 142.7, 153.0, 154.5, 193.8. HRMS (EI) calcd for C11H15NOSi 205.0923, found 205.0927.

Workup

  1. additionwas added over a period of 5 min
  2. additionSaturated NCl (10 mL) was added to the reaction mixture
  3. customThe layers were separated
  4. dry with materialthe organic layer was dried (Na2SO4)
  5. concentrationconcentrated
  6. customThe crude product was purified by column chromatography (1:7 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-ad70ac1468394dd78eabb1b8a1e13341
Source dataset
uspto-grants-2002_07
Patent number
US06416861B1

Reaction notes

Loading…