Pyridine, hydrofluoride (1:1) → HCID 58520797、化合物

HRID 244500ノート

反応式

HRID 244500 の反応式
[CH2:1]([O:8][C:9]([NH:11][CH:12]1[CH2:14][C:13]1([O:20][Si](C(C)(C)C)(C)C)[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.F.N1C=CC=CC=1>C1COCC1.CCOCC>[CH2:1]([O:8][C:9]([NH:11][CH:12]1[CH2:14][C:13]1([OH:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

5

反応物 2

HCID 64774Pyridine, hydrofluoride (1:1)2 回HCID 66728242Ethyl 2-(benzyloxycarbonylamino)-1-(tert-butyldimethylsilyloxy)cyclopropanecarboxylate

生成物 1

HCID 58520797HCID 58520797、化合物収率 93.2%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a solution of ethyl 2-(benzyloxycarbonylamino)-1-(tert-butyldimethylsilyloxy)cyclopropanecarboxylate (1.45 g, 3.69 mmol) in THF (35 mL) under N7 was added HF·pyridine (1.0 mL, 38 mmol). The reaction mixture was stirred for 5 h. After this time, additional HF·pyridine (1.0 mL, 38 mmol) was added and stirring was continued for 19 h. The reaction mixture was then cooled to 0° C. and diluted with Et2O (150 mL). The mixture was then carefully quenched with saturated aqueous NaHCO3 until gas evolution ceased. At this time, the organic layer was separated and the remaining aqueous layer was extracted with Et2O (300 mL). The combined organic layers were washed with brine (200 mL), dried (Na2SO4), filtered, and concentrated in vacuo. Purification by silica gel chromatography eluting with 20%-50% EtOAc/hexanes afforded the title compound (0.960 g, 93%): 1H NMR (300 MHz, CDCl3) δ 7.34-7.30 (m, 5H), 5.11-4.83 (m, 3H), 4.21 (q, J=7.2 Hz, 2H), 3.37-3.25 (m, 2H), 1.73-1.68 (m, 1H), 1.27 (t, J=7.2 Hz, 3H), 1.14-1.06 (m, 1H); ESI MS m/z 280 [M+H]+.

後処理

  1. stirringstirring
  2. waitwas continued for 19 h
  3. customThe mixture was then carefully quenched with saturated aqueous NaHCO3 until gas evolution
  4. customAt this time, the organic layer was separated
  5. extractionthe remaining aqueous layer was extracted with Et2O (300 mL)
  6. washThe combined organic layers were washed with brine (200 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customPurification by silica gel chromatography
  11. washeluting with 20%-50% EtOAc/hexanes

出典と根拠

ORDレコード
ord-a2917ab7850b4d08b6944993bc05f532
出典データセット
uspto-grants-2014_02
特許番号
US08658606B2

反応ノート

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