Potassium Carbonate → tert-Butyl 3-(acetylthio)pyrrolidine-1-carboxylate

HRID 2421965ノート

反応式

HRID 2421965 の反応式
C(=O)([O-])[O-].[K+].[K+].[C:7]([OH:10])(=[S:9])[CH3:8].CS(O[CH:16]1[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17]1)(=O)=O>CO.CN(C=O)C.O>[C:7]([S:9][CH:20]1[CH2:16][CH2:17][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:19]1)(=[O:10])[CH3:8]

参加物

7

反応物 3

HCID 11430Potassium CarbonateHCID 4139999Tert-butyl 3-(methanesulfonyloxy)pyrrolidine-1-carboxylateHCID 178418634HCID 178418634、化合物

生成物 1

HCID 54776232tert-Butyl 3-(acetylthio)pyrrolidine-1-carboxylate収率 24.2%

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
60 °C

実験手順

Potassium carbonate (4.42 g, 31.96 mmol) was suspended in dry MeOH (20 mL) and thioacetic acid (2.28 g, 29.96 mmol) was added. The mixture was stirred vigorously for 10 mins, concentrated and diluted in dry DMF (30 mL). tert-Butyl 3-[(methylsulfonyl)oxy]pyrrolidine-1-carboxylate (2.65 g, 9.99 mmol) dissolved in dry DMF (20 mL) was added and the reaction mixture was heated to 60° C. for 3.5 h. The reaction mixture was diluted with water (350 mL) and extracted with EtOAc (2×150 mL) The organic phases were dried with MgSO4, filtered and evaporated. The crude product was purified using Biotage Horizon HPFC system (25+M column, isocratic run heptane/EtOAc (60:40)) affording the title compound (0.592 g, 24.2%) (the product is a mixture of cis and trans isomers). 1H NMR (500 MHz, CDCl3): δ 1.41 (d, 18H), 1.66 (d, 1H), 1.74-1.86 (m, 2H), 2.20-2.26 (m, 2H), 2.29 (s, 3H), 3.10-3.26 (m, 2H), 3.30-3.43 (m, 4H), 3.46-3.54 (m, 1H), 3.66-3.74 (m, 2H); 13C NMR (125 MHz, CDCl3): δ 28.68, 30.82, 31.25, 32.34, 36.16, 41.09, 44.88, 51.60, 55.37, 79.67, 154.43; Mass Spectrum: M+H+ 241.

後処理

  1. concentrationconcentrated
  2. additiondiluted in dry DMF (30 mL)
  3. additionwas added
  4. extractionextracted with EtOAc (2×150 mL) The organic phases
  5. dry with materialwere dried with MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified

出典と根拠

ORDレコード
ord-eb3cb61d2dcd42cea6efae5c13e9ac4d
出典データセット
uspto-grants-2011_06
特許番号
US07960380B2

反応ノート

読み込み中…