Diethyl Ether → benzyl[(2S)-1-{[tert-butyl(diphenyl)silyl]oxy}-5-fluoro-6-oxohexan-2-yl](3-methylbutyl)carbamate

HRID 1524349ノート

反応式

HRID 1524349 の反応式
C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:11])(=O)=O)=CC=1.[CH2:21]([O:28][C:29](=[O:61])[N:30]([C@@H:36]([CH2:56][CH2:57][CH2:58][CH:59]=[O:60])[CH2:37][O:38][Si:39]([C:52]([CH3:55])([CH3:54])[CH3:53])([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)[CH2:31][CH2:32][CH:33]([CH3:35])[CH3:34])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.CCOCC>CC(O)C.C1COCC1>[CH2:21]([O:28][C:29](=[O:61])[N:30]([C@@H:36]([CH2:56][CH2:57][CH:58]([F:11])[CH:59]=[O:60])[CH2:37][O:38][Si:39]([C:52]([CH3:53])([CH3:54])[CH3:55])([C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)[C:46]1[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=1)[CH2:31][CH2:32][CH:33]([CH3:34])[CH3:35])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

参加物

5

反応物 3

HCID 3283Diethyl EtherHCID 588007N-FluorobenzenesulfonimideHCID 86708051benzyl[(2S)-1-{[tert-butyl(diphenyl)silyl]oxy}-6-oxohexan-2-yl](3-methylbutyl)carbamate

生成物 1

HCID 89916921benzyl[(2S)-1-{[tert-butyl(diphenyl)silyl]oxy}-5-fluoro-6-oxohexan-2-yl](3-methylbutyl)carbamate

試薬・触媒・溶媒 1

HCID 22597222Tetrahydrofuran 2-propanol溶媒2 回

反応条件

温度
-20 °C

実験手順

Racemic 5-benzyl-2-2,3-trimethylimidazolidin-4-one dichloroacetic acid (109 mg, 0.314 mmol) and N-fluorobenzenesulfonimide (593 mg, 1.88 mmol) were dissolved in 10% i-PrOH-THF (3.75 mL). The reaction mixture was cooled to −20° C., and the compound from Step 7 (900 mg, 1.57 mmol) in 1.25 mL of 10% i-PrOH-THF was added. The reaction mixture was stirred at −20° C. for 24 hours, 2 volumes of ether were added, and the resulting mixture was vigorously stirred, filtered through Davisil® silica (W.R. Grace & Co.-Conn.), and eluted with ether. 5 mL of methyl sulfide was added to the eluted reaction mixture. The reaction mixture was partitioned between EtOAc and saturated aqueous NaHCO3 and extracted with EtOAc (2×). The combined organics were washed with brine, dried over MgSO4, filtered and concentrated in vacuo to afford the title compound which was used directly at Step 9. 1H NMR (DMSO-d6): δ7.66-7.52 (m, 5H), 7.51-7.25 (m, 10H), 5.08 (s, 2H), 4.90-4.83 (m, 1H), 3.70-3.55 (m, 1H), 3.53-3.36 (m, 2H), 3.17-2.99 (m, 2H), 1.63-1.32 (m, 7H), 0.96 (s, 9H), 0.88-0.72 (m 6H), aldehyde signal missing due to hydrate form.

後処理

  1. stirringthe resulting mixture was vigorously stirred
  2. filtrationfiltered through Davisil® silica (W.R. Grace & Co.-Conn.)
  3. washeluted with ether
  4. addition5 mL of methyl sulfide was added to the eluted reaction mixture
  5. customThe reaction mixture was partitioned between EtOAc and saturated aqueous NaHCO3
  6. extractionextracted with EtOAc (2×)
  7. washThe combined organics were washed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-2cd5724d397a4c03bac236b2269040ef
出典データセット
uspto-grants-2015_07
特許番号
US09079834B2

反応ノート

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