(Triethylsilyl)acetylene → 5-[(Triethylsilyl)ethynyl]-1H-indole

HRID 2191078Notes

Reaction equation

HRID 2191078 reaction equation
I[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[CH:5]2.[CH2:11]([Si:13]([C:18]#[CH:19])([CH2:16][CH3:17])[CH2:14][CH3:15])[CH3:12]>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH2:14]([Si:13]([C:11]#[C:12][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[CH:5]2)([CH2:18][CH3:19])[CH2:16][CH3:17])[CH3:15]

Participants

6

Reactant 2

HCID 637947(Triethylsilyl)acetyleneHCID 27823135-Iodo-1H-indole

Product 1

HCID 668932335-[(Triethylsilyl)ethynyl]-1H-indoleYield 101.8%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Procedure

To a stirred solution of 5-iodoindole (0.50 g, 2.0 mmol) and (triethylsilyl)-acetylene (0.58 g, 4.0 mmol) in diisopropylamine (15 mL) was added Pd(PPh3)2Cl2 (0.07 g, 0.10 mmol) and CuI (0.04 g, 0.20 mmol) and the reaction mixture was stirred at r.t. for 16 h. The solvent was then removed in vacuo. EtOAc (15 mL) and water (15 mL) were added and the layers separated. The aqueous layer was extracted with EtOAc (2×10 mL). The combined organic layers were washed with water (2×20 mL), dried (Na2SO4), filtered and concentrated in vacuo. Purification by column chromatography (SiO2, 10% EtOAc/hexanes) gave the title compound (0.52 g, quantitative). δH (DMSO-d6) 11.30 (1H, br. s), 7.69 (1H, s), 7.45-7.41 (1H, m), 7.37 (1H, d, J 8.4 Hz), 7.15 (1H, dd, J 8.4 and 1.5 Hz), 6.48-6.40 (1H, m), 1.02 (9H, t, J 7.8 Hz), 0.65 (6H, q, J 7.9 Hz). MS (ES−) 254.0 (M−H)−.

Workup

  1. customThe solvent was then removed in vacuo
  2. additionEtOAc (15 mL) and water (15 mL) were added
  3. customthe layers separated
  4. extractionThe aqueous layer was extracted with EtOAc (2×10 mL)
  5. washThe combined organic layers were washed with water (2×20 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification by column chromatography (SiO2, 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-96bb1b246ef1438bbb96cb715b821699
Source dataset
uspto-grants-2012_12
Patent number
US08324204B2

Reaction notes

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