Ethyl diazoacetate → Ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylate

HRID 1039967

反応式

HRID 1039967 の反応式
[C:1]([Si:5]([O:8][CH:9]1[CH2:13][CH:12]=[CH:11][CH2:10]1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[N+](=[CH:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N-]>CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[Si:5]([O:8][CH:9]1[CH2:13][CH:12]2[CH:11]([CH:16]2[C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:10]1)([C:1]([CH3:4])([CH3:2])[CH3:3])([CH3:7])[CH3:6]

参加物

4

反応物 2

HCID 12192Ethyl diazoacetateHCID 11106335Tert-butyl(cyclopent-3-en-1-yloxy)dimethylsilane

生成物 1

HCID 67432091Ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylate収率 73%

試薬・触媒・溶媒 1

HCID 152122Dirhodium tetraacetate触媒

実験手順

To a flask was added tert-butyl(cyclopent-3-en-1-yloxy)dimethylsilane (0.5 g, 2.52 mmol) and rhodium(II) acetate dimer (22 mg, 0.05 mmol). The flask was evacuated and purged 5 times with argon. Dichloromethane (8.4 mL) was added and the flask was evacuated and purged 5 times with argon. In a separate flask, ethyl diazoacetate (0.37 mL, 3.02 mmol) was added. The flask was evacuated and purged with argon five times. Dichloromethane (8.4 mL) was added and the solution was added to the first flask via syringe pump over a six hour time period and then allowed to stir overnight. The mixture was filtered over a pad of celite and then concentrated. Flash chromatography was used for purification to yield ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylate (524 mg, 1.84 mmol, 73% yield). 1H NMR (500 MHz, CDCl3) δ 4.13-4.03 (m, 2H), 2.37-2.20 (m, 1H), 2.20-2.12 (m, 1H), 2.11-1.96 (m, 1H), 1.94-1.70 (m, 4H), 1.35-1.14 (m, 4H), 0.89-0.79 (m, 9H), 0.05-−0.11 (m, 6H).

後処理

  1. customThe flask was evacuated
  2. custompurged 5 times with argon
  3. additionDichloromethane (8.4 mL) was added
  4. customthe flask was evacuated
  5. custompurged 5 times with argon
  6. customThe flask was evacuated
  7. custompurged with argon five times
  8. additionDichloromethane (8.4 mL) was added
  9. additionthe solution was added to the first flask via syringe pump over a six hour time period
  10. filtrationThe mixture was filtered over a pad of celite
  11. concentrationconcentrated
  12. customFlash chromatography was used for purification

出典と根拠

ORDレコード
ord-09d7558bbcad488f8404b748a15b9211
出典データセット
uspto-grants-2013_10
特許番号
US08551984B2

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