Sodium Hydroxide → cis-4-Tert-butyloxy-cyclopent-2-enol

HRID 2548

反応式

HRID 2548 の反応式
[H-].[Al+3].[Li+].[H-].[H-].[H-].[I-].[Li+].[C:9]([O:13][CH:14]1[CH2:18][C:17](=[O:19])[CH:16]=[CH:15]1)([CH3:12])([CH3:11])[CH3:10].[OH-].[Na+]>C1(C)C=CC=CC=1.COC(C)(C)C>[C:9]([O:13][C@@H:14]1[CH2:18][C@H:17]([OH:19])[CH:16]=[CH:15]1)([CH3:12])([CH3:10])[CH3:11]

参加物

7

反応物 4

HCID 14798Sodium HydroxideHCID 66321Lithium iodideHCID 110625964-Tert-butoxy-cyclopent-2-enoneHCID 21226445Aluminium lithium hydride

生成物 1

HCID 11789450cis-4-Tert-butyloxy-cyclopent-2-enol収率 42%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 15413tert-Butyl methyl ether溶媒

実験手順

A slurry of lithium aluminum hydride (55 mg, 1.44 mmol), lithium iodide (1.65 g, 5.76 mmol), tert-butyl methyl ether (2 mL) and toluene (3 mL) is cooled to -15° C. The slurry is treated dropwise with 4-tert-butoxy-cyclopent-2-enone(430 mg, 2.79 mmol, dissolved in 1 mL of toluene) over 5 minutes. The reaction mixture is stirred at -20° C. to -12° C. for 2 hours and then allowed to warm to room temperature and is stirred for 30 minutes. The reaction mixture is then treated sequentially with sodium hydroxide (1N, 1 mL), then tert-butyl methyl ether (10 mL) and filtered. The phases of the filtrate are separated and the aqueous phase is extracted with tert-butyl methyl ether (15 mL). The organic extracts and organic phase is combined, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue is purified by chromatography (silica gel, 30 g, 33% ethyl acetate/hexane) to provide the title compound (183 mg, 42%) as a yellow oil, cis/trans/1-2+1-4 addition, 87/9.8/3.2; 1H NMR (CDCl3) 6 5.9 (m, 1H), 5.8 (m, 1H), 4.6 (m, 1H), 4.5 (m, 1H), 2.7 (m, 1H), 2.0 (d,1H, J=9.6 Hz), 1.5 (d appt, 1H, J=4.5, 14 Hz), 1.2 (s, 9H); 13C NMR (CDCl3) δ136.6, 36, 75.5, 74.4, 74, 44.6, 28.7; νmax 3395, 2974, 2938, 907, 2878, 1389, 1364, 1117, 1169, 1022 cm-1 ; MS (CI) m/e (% relative intensity) 157 (M+H+ -H2O), 57, 83 (100).

後処理

  1. stirringis stirred for 30 minutes
  2. filtrationtert-butyl methyl ether (10 mL) and filtered
  3. customThe phases of the filtrate are separated
  4. extractionthe aqueous phase is extracted with tert-butyl methyl ether (15 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residue is purified by chromatography (silica gel, 30 g, 33% ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-e0e346db372f42efa4e13b85899186f1
出典データセット
uspto-grants-1998_03
特許番号
US05728899

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