Triethylamine → ethyl N-[(4-chloro-3-trimethylsilylethynylphenyl)methyl]-5-acetoxyindole-2-carboxylate

HRID 1610932Notes

Reaction equation

HRID 1610932 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][N:15]2[C:23]3[C:18](=[CH:19][C:20]([O:24][C:25](=[O:27])[CH3:26])=[CH:21][CH:22]=3)[CH:17]=[C:16]2[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:10][C:9]=1I.C(N(CC)CC)C>C(#N)C.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.[Cu]I>[Cl:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:14][N:15]2[C:23]3[C:18](=[CH:19][C:20]([O:24][C:25](=[O:27])[CH3:26])=[CH:21][CH:22]=3)[CH:17]=[C:16]2[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:12][C:13]=1[C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111Trimethylsilylacetylene3×HCID 22259365Ethyl N-[(4-chloro-3-iodophenyl)methyl]-5-acetoxyindole-2-carboxylate

Product 1

HCID 22259369ethyl N-[(4-chloro-3-trimethylsilylethynylphenyl)methyl]-5-acetoxyindole-2-carboxylate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalyst2×HCID 6342AcetonitrileSolvent

Procedure

Trimethylsilylacetylene (114 il) was added to a degassed solution of ethyl N-[(4-chloro-3-iodophenyl) methyl]-5-acetoxyindole-2-carboxylate (0.2 g), bis(triphenylphosphine)palladium (II) chloride (2 mg), triethylamine (56 il) and copper (I) iodide (1 mg) in acetonitrile and the mixture was stirred under an argon atmosphere for 12 hours. A further aliquot of bis(triphenylphosphine)palladium (II) chloride (2 mg) and trimethylsilylacetylene (114 il) was added and stirring continued for 2 hours. A further aliquot of trimethylsilylacetylene (114 il) was added and stirring was continued for 12 hours. A small amount of silica was added to the reaction mixture and the solvent was evaporated. The residue was added to a 5 g silica Isolute column and eluted with an ethyl acetate iso-hexane mixture (1:4) to give the title compound as a colourless oil (0.15 g). NMR (CD3SOCD3): d 0.0 (s, 9H), 1.1 (t, 31H), 2.1 (s, 3H), 4.1 (m, 2H), 5.6 (s, 2H), 6.7 (m, 2H), 6.9 (m, 2H), 7.1 (m, 1H), 7.2 (m, 2H), 7.3 (n, 1H), 7.4 (m, 1H); m/z 468.5 (M+H).

Workup

  1. stirringstirring
  2. waitcontinued for 2 hours
  3. stirringstirring
  4. waitwas continued for 12 hours
  5. additionA small amount of silica was added to the reaction mixture
  6. customthe solvent was evaporated
  7. additionThe residue was added to a 5 g silica Isolute column
  8. washeluted with an ethyl acetate iso-hexane mixture (1:4)

Sources & evidence

ORD record
ord-e5b0e42ddbb64ace861f9b9166314dc7
Source dataset
uspto-grants-2006_01
Patent number
US06984657B1

Reaction notes

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