Triethylamine → 3-Chloro-5-[2-(trimethylsilyl)ethynyl]pyridine

HRID 606806Notes

Reaction equation

HRID 606806 reaction equation
C(N(CC)CC)C.[CH3:8][Si:9]([C:12]#[CH:13])([CH3:11])[CH3:10].[Cl:14][C:15]1[CH:16]=[C:17](OS(C(F)(F)F)(=O)=O)[CH:18]=[N:19][CH:20]=1>C(OCC)(=O)C.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[Cl:14][C:15]1[CH:20]=[N:19][CH:18]=[C:17]([C:13]#[C:12][Si:9]([CH3:11])([CH3:10])[CH3:8])[CH:16]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 151858705-Chloropyridin-3-yl trifluoromethanesulfonate

Product 1

HCID 235008913-Chloro-5-[2-(trimethylsilyl)ethynyl]pyridineYield 92.5%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

Sequentially add triethylamine (16 mL, 114 mmol), trimethylsilyl acetylene (4.5 mL, 34.1 mmol), bis(triphenylphosphine)palladium (II) dichloride (0.538 g, 0.77 mmol), and copper (I) iodide (270 mg, 1.42 mmol) to a solution of trifluoromethanesulfonic acid 5-chloropyridin-3-yl ester (7.4 g, 28.4 mmol), (prepared as described in PREPARATION 25), in ethyl acetate (25 mL) under nitrogen. Heat at 60° C. for 1 h, cool to room temperature, stir for 12 h, filter through diatomaceous earth and wash with diethyl ether. Concentrate and purify the residue by silica gel chromatography, eluting with 20:80 ethyl acetate:hexanes, to give the title compound as an orange oil (5.51 g, 92%).

Workup

  1. temperaturecool to room temperature
  2. filtrationfilter through diatomaceous earth
  3. washwash with diethyl ether
  4. concentrationConcentrate
  5. custompurify the residue by silica gel chromatography
  6. washeluting with 20:80 ethyl acetate

Sources & evidence

ORD record
ord-db970152b47f4ec48f87debacf0ba9c4
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

Loading…