1-(Trimethylsilyl)prop-1-yne → HCID 57856278, compound

HRID 500719Notes

Reaction equation

HRID 500719 reaction equation
[Br:1][C:2]1[CH:3]=[C:4](I)[C:5]([NH2:8])=[N:6][CH:7]=1.CC([O-])=O.[K+].[Li+].[Cl-].[CH3:17][Si:18]([CH3:23])([CH3:22])[C:19]#[C:20][CH3:21]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]2[C:20]([CH3:21])=[C:19]([Si:18]([CH3:23])([CH3:22])[CH3:17])[NH:8][C:5]2=[N:6][CH:7]=1

Participants

8

Reactant 4

HCID 803631-(Trimethylsilyl)prop-1-yneHCID 433294Lithium ChlorideHCID 517044Potassium AcetateHCID 15165082-Amino-5-bromo-3-iodopyridine

Product 1

HCID 57856278HCID 57856278, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 5-bromo-3-iodopyridin-2-amine (B-5-2) (30 g, 0.1 mol) in DMF (600 mL) were added KOAc (29.4 g, 0.3 mol) and LiCl (4.25 g, 0.1 mol). After the mixture was degassed under N2 for 3 times, Pd(OAc)2 (2.24 g, 0.01 mol) was added, and the mixture was degassed again. Then trimethyl-prop-1-ynyl-silane (56 g, 0.5 mol) was added. The resulting mixture was heated to 80-100° C. for 2 days. TLC (EtOAc: Petroleum ether=1:5) showed that the reaction was complete. Excess DMF was removed under reduced pressure. The residue was dissolved in EtOAc (500 mL), washed with saturated aqueous NaCl, dried over Na2SO4 and concentrated to give crude product, which was purified via a silica gel column chromatography (100-200) (Petroleum ether, then EtOAc:Petroleum ether=1:10) to give 5-bromo-3-methyl-2-(trimethylsilyl)-1H-pyrrolo[2,3-b]pyridine (B-5-3) (not pure, 5 g, 17.7%) as a brown oil.

Workup

  1. additionwas added
  2. customthe mixture was degassed again
  3. customExcess DMF was removed under reduced pressure
  4. dissolutionThe residue was dissolved in EtOAc (500 mL)
  5. washwashed with saturated aqueous NaCl
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customto give crude product, which
  9. customwas purified via a silica gel column chromatography (100-200) (Petroleum ether

Sources & evidence

ORD record
ord-0d97ca51ace54851a384a4feabdc8e7a
Source dataset
uspto-grants-2010_08
Patent number
US07772246B2

Reaction notes

Loading…