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

HRID 2393907

반응식

HRID 2393907 반응식
[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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
-20 °C

실험 절차

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) δ 7.5 (m, 6 H), 7.3 (m, 9 H), 5.79 (d, 1 H), 5.14 (d, 1 H), 4.5 (m, 1 H), 4.4 (m, 1 H), 2.2 (m, 1 H), 1.42 (d, 1 H); 13C NMR (CDCl3) δ 145.1, 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. Example 28a

후처리

  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)

출처 및 근거

ORD 기록
ord-59602782c691486ba36a1986b47f7159
출처 데이터셋
uspto-grants-1998_09
특허 번호
US05808112

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