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

HRID 410475

Reaction equation

HRID 410475 reaction equation
[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]

Participants

4

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 152122Dirhodium tetraacetateCatalyst

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-dab51de320b24321ac6de06e3d29b1b4
Source dataset
uspto-grants-2014_06
Patent number
US08759366B2

Linked notes

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