tert-Butyl methyl ether → (+/-)-cis-4-Trityloxy-2-cyclopentenol

HRID 2564

反応式

HRID 2564 の反応式
[C:1]([O:20][CH:21]1[CH2:25][C:24](=[O:26])[CH:23]=[CH:22]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[I-].[Li+].COC(C)(C)C>C1(C)C=CC=CC=1>[C:1]([O:20][C@@H:21]1[CH2:25][C@H:24]([OH:26])[CH:23]=[CH:22]1)([C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

6

反応物 4

HCID 15413tert-Butyl methyl etherHCID 66321Lithium iodideHCID 109914404-Trityloxy-2-cyclopentenoneHCID 21226445Aluminium lithium hydride

生成物 1

HCID 10980801(+/-)-cis-4-Trityloxy-2-cyclopentenol収率 95%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
-20 °C

実験手順

A slurry of 4-trityloxy-2-cyclopentenone (1.03 g, 3.03 mmol, prepared in example 27) in toluene (8 mL) is cooled to -20° C. and treated sequentially with lithium aluminum hydride (76 mg, 2.0 mL), lithium iodide (1.06 g, 7.9 mmol) and dropwise with tert-butyl methyl ether (2 mL, over 5 minutes). The reaction is stirred for 1 hour at -20° C., warmed to 0° C. over 30 minutes, and stirred at 0° C. to 15° C. for 4 hours. The reaction is quenched by slow addition of 1N NaOH (2 mL) and then the reaction is filtered. The solids are washed with tert-butyl methyl ether and the phases of the filtrate are separated. The organic phase is dried over anhydrous magnesium sulfate, filtered and concentrated under vacuum. The residue is purified by column chromatography (silica gel, 20% ethyl acetate/hexane) to provide the title compound as a white foam (980 mg, 95%). 1H NMR (CDCl3) δ7.5 (m, 6H), 7.3 (m, 9H), 5.79 (d, 1H), 5.14 (d, 1H), 4.5 (m, 1H), 4.4 (m, 1H), 2.2 (m, 1H), 1.42 (d, 1H); 13C NMR (CDCl3) δ145.1, 136.2, 135.9, 129.0, 128.1, 127.3, 87.7, 77.4, 74.9, 43.2; IR (KBr) νmax 3422, 3057, 1491, 1364, 1084, 1065, 1024 cm-1.

後処理

  1. temperaturewarmed to 0° C. over 30 minutes
  2. stirringstirred at 0° C. to 15° C. for 4 hours
  3. customThe reaction is quenched by slow addition of 1N NaOH (2 mL)
  4. filtrationthe reaction is filtered
  5. washThe solids are washed with tert-butyl methyl ether
  6. customthe phases of the filtrate are separated
  7. dry with materialThe organic phase is dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum
  10. customThe residue is purified by column chromatography (silica gel, 20% ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-802e8dff62b74fa49096ebf9f90abcb7
出典データセット
uspto-grants-1998_03
特許番号
US05728899

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