Water → HCID 58979654、化合物

HRID 1180730ノート

反応式

HRID 1180730 の反応式
[CH2:1]([C:8]1([O:13][C:14]([NH:16][C@@H:17]([CH2:22][CH2:23][CH2:24][CH3:25])[C:18](OC)=[O:19])=[O:15])[CH2:12][CH2:11][CH2:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.[OH-].[Li+].[C:29]1([P:35](=[CH:48][C:49]#[N:50])([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.O>O1CCCC1.O.CN(C)C1C=CN=CC=1>[C:49]([C:48](=[P:35]([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)([C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)[C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)[C:18]([C@@H:17]([NH:16][C:14](=[O:15])[O:13][C:8]1([CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:12][CH2:11][CH2:10][CH2:9]1)[CH2:22][CH2:23][CH2:24][CH3:25])=[O:19])#[N:50]

参加物

7

反応物 4

HCID 962WaterHCID 85524(Triphenylphosphoranylidene)acetonitrileHCID 168937Lithium hydroxide, monohydrateHCID 58979699HCID 58979699、化合物

生成物 1

HCID 58979654HCID 58979654、化合物収率 34%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 21881883Oxolane--water (1/1)溶媒

実験手順

To 1.31 g (3.77 mmol) of methyl(2S)-2-({[(1-benzylcyclopentyl)oxy]carbonyl}amino)hexanoate in 12 mL of tetrahydrofuran:water (1:1) was added 221.5 mg (5.28 mmol) of lithium hydroxide monohydrate and the mixture was stirred at room temperature for 4 h. The solution was concentrated and extracted with ethyl acetate. The aqueous layer was acidified with 1 N hydrochloric acid and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and concentrated. The residue was dissolved in 19 mL of dichloromethane, then 23.0 mg (188.5 μmol) of 4-dimethylaminopyridine was added. To this solution was added 1.19 g (3.96 mmol) of (triphenylphosphoranylidene)acetonitrile, followed by 799.2 mg (4.15 mmol) of 1-ethyl-3-(3-dimethyl-aminopropyl)carbodiimide, and the mixture was stirred at room temperature for 19 h. Water was added to the solution and it was extracted with ethyl acetate. The organic layer was washed with 10% citric acid, followed by saturated sodium bicarbonate, and saturated sodium chloride. The organic layer was dried over magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography eluting with an ethyl acetate:hexanes solution (1:1) to give 789.8 mg (34%) of 1-benzylcyclopentyl(1S)-1-[cyano(triphenylphosphoranylidene)acetyl]pentylcarbamate. Rf=0.31 (1:1 ethyl acetate:hexanes); 1H NMR (300 MHz, DMSO-d6) δ 7.76-7.66 (m, 3H), 7.64-7.54 (m, 12H), 7.20-7.14 (m, 5H), 6.90 (d, J=8 Hz, 1H), 4.58-4.50 (m, 1H), 3.24 (ABq, JAB=14 Hz, ΔνAB=31 Hz, 2H), 1.88-1.66 (m, 4H), 1.64-1.44 (m, 6H),1.42-1.14 (m, 4H), 0.89 (t, J=7 Hz, 3H); ES-LCMS m/z 617 (M+H).

後処理

  1. concentrationThe solution was concentrated
  2. extractionextracted with ethyl acetate
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe residue was dissolved in 19 mL of dichloromethane
  8. stirringthe mixture was stirred at room temperature for 19 h
  9. extractionwas extracted with ethyl acetate
  10. washThe organic layer was washed with 10% citric acid
  11. dry with materialThe organic layer was dried over magnesium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customThe residue was purified by silica gel column chromatography
  15. washeluting with an ethyl acetate

出典と根拠

ORDレコード
ord-8d7cbae7b9b641a88380a9ead1ba9cc4
出典データセット
uspto-grants-2007_10
特許番号
US07282512B2

反応ノート

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