Triethylamine → 2-(Trimethylsilyl)furo[3,2-b]pyridine

HRID 1470334Notes

Reaction equation

HRID 1470334 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].Br[C:8]1[C:13]([OH:14])=[CH:12][CH:11]=[CH:10][N:9]=1.C(N(CC)CC)C>O1CCOCC1.[Cu]I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH3:4][Si:3]([CH3:6])([CH3:5])[C:1]1[O:14][C:13]2[C:8](=[N:9][CH:10]=[CH:11][CH:12]=2)[CH:2]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 230702-Bromo-3-pyridinolHCID 66111Trimethylsilylacetylene

Product 1

HCID 136365392-(Trimethylsilyl)furo[3,2-b]pyridineYield 100.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
500 °C

Procedure

Ethynyltrimethylsilane (32.5 ml, 0.2298 mol), copper(I)iodide (2.2 g, 0.0114 mol) and bis(triphenylphospine)palladium(II)chloride (4.1 g, 0.0057 mol) are added to a degassed solution of 2-Bromopyridine-3-ol (20 g, 0.1149 mol) in dioxane (20 ml). The mixture is stirred for 5 min under nitrogen and then triethyl amine (80 ml, 0.574 7 mol) is added. The mixture is heated to 500° C. for 18 h, cooled to RT, filtered through celite and the filtrate is concentrated under reduced pressure. The crude material is purified by column chromatography by using petrolether and ethyl acetate (90:10) as an eluent to afford (22 g, 56%) of the title compound as a brown liquid. TLC: hexane/ethyl acetate: (9/1): Rf=0.50; LCMS (method B): 4.875 min (purity 98.4%); M+H+ 192.1; 1H NMR (DMSO-d6, 400 MHz) δ [ppm] 8.50-8.48 (1H, dd, J1=1 Hz, J2=4.6 Hz), 8.015-7.9923 (1H, dd, J1=1 Hz, J2=8.32 Hz), 7.352-7.350 (1H, d, J1=0.8 Hz), 7.314-7.280 (1H, m), 0.372-0.355 (9H, s).

Workup

  1. temperaturecooled to RT
  2. filtrationfiltered through celite
  3. concentrationthe filtrate is concentrated under reduced pressure
  4. customThe crude material is purified by column chromatography

Sources & evidence

ORD record
ord-d03d5ad6da324706984d02756fa5e61f
Source dataset
uspto-grants-2015_04
Patent number
US09006440B2

Reaction notes

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