Triethylamine → (S)-tert-butyl (5-{[5-({[methyl(oxo)phenyl-lambda6-sulfanylidene]amino}carbonyl)pyridin-3-yl]ethynyl}-1,3-thiazol-2-yl)carbamate

HRID 1099647ノート

反応式

HRID 1099647 の反応式
[CH3:1][S:2](=[O:24])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[N:3][C:4](=[O:17])[C:5]1[CH:10]=[C:9]([C:11]#[C:12][Si](C)(C)C)[CH:8]=[N:7][CH:6]=1.Br[C:26]1[S:30][C:29]([NH:31][C:32](=[O:38])[O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[N:28][CH:27]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[H][H].N#N.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CN(C=O)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>[CH3:1][S@:2](=[N:3][C:4]([C:5]1[CH:10]=[C:9]([C:11]#[C:12][C:26]2[S:30][C:29]([NH:31][C:32](=[O:38])[O:33][C:34]([CH3:36])([CH3:35])[CH3:37])=[N:28][CH:27]=2)[CH:8]=[N:7][CH:6]=1)=[O:17])(=[O:24])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

参加物

10

反応物 6

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 2724141Tetrabutylammonium FluorideHCID 21300388tert-butyl N-(5-bromo-1,3-thiazol-2-yl)carbamateHCID 57657915N-[methyl(oxo)phenyl-lambda6-sulfanylidene]-5-[(trimethylsilyl)ethynyl]nicotinamideHCID 178514468HCID 178514468、化合物

生成物 1

HCID 24954183(S)-tert-butyl (5-{[5-({[methyl(oxo)phenyl-lambda6-sulfanylidene]amino}carbonyl)pyridin-3-yl]ethynyl}-1,3-thiazol-2-yl)carbamate収率 18%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒

実験手順

A mixture of N-[methyl(oxo)phenyl-λ6-sulfanylidene]-5-[(trimethylsilyl)ethynyl]nicotinamide (73 mg, 0.21 mmol), tert-butyl (5-bromo-1,3-thiazol-2-yl)carbamate (74 mg, 0.27 mmol), dichlorobis(triphenylphosphine)palladium(II) (14 mg, 0.02 mmol), triphenylphosphine (2.7 mg, 0.004 mmol) and triethylamine (0.071 mL, 0.51 mmol) in 1.8 mL DMF at room temperature was degassed using vacuum and a H2/N2 (1:1) mixture and then copper(I)iodide (2 mg, 0.01 mmol) added. While stirring the mixture at room temperature, tetrabutylammonium fluoride (1.0 M in THF, 0.21 mL) was added over 2.5 minutes. After 5 minutes the reaction was heated at 60° C. for 2 hours. The reaction was partitioned between EtOAc and H2O and the EtOAc layer washed with H2O, aqueous HCl, saturated NaHCO3 solution, brine, dried with anhydrous Na2SO4 and concentrated. The brown oil was chromatographed eluting with hexane/acetone and the product containing fractions were concentrated to give the title compound as a light yellow solid (17 mg, 18%).

後処理

  1. customwas degassed
  2. temperatureAfter 5 minutes the reaction was heated at 60° C. for 2 hours
  3. customThe reaction was partitioned between EtOAc and H2O
  4. washthe EtOAc layer washed with H2O, aqueous HCl, saturated NaHCO3 solution, brine
  5. dry with materialdried with anhydrous Na2SO4
  6. concentrationconcentrated
  7. customThe brown oil was chromatographed
  8. washeluting with hexane/acetone
  9. additionthe product containing fractions
  10. concentrationwere concentrated

出典と根拠

ORDレコード
ord-e8fa4e0afc5e4c81b8f7a4a769ddb07f
出典データセット
uspto-grants-2012_03
特許番号
US08143410B2

反応ノート

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