Ethyl diazoacetate → Ethyl 2-(bromomethyl)-3-phenylcyclopropanecarboxylate

HRID 1826420Notes

Reaction equation

HRID 1826420 reaction equation
[Br:1][CH2:2]/[CH:3]=[CH:4]/[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[N+](=[CH:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])=[N-]>ClCCl.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.[Rh].[Rh]>[Br:1][CH2:2][CH:3]1[CH:4]([C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH:13]1[C:14]([O:16][CH2:17][CH3:18])=[O:15]

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetateHCID 5357478Cinnamyl bromide

Product 1

HCID 22141265Ethyl 2-(bromomethyl)-3-phenylcyclopropanecarboxylateYield 8%

Reagents, catalysts & solvents 2

HCID 423677Acetic acid, rhodium salt (4:2)CatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of [(E)-3-bromo-1-propenyl]benzene (705 mg, 3.58 mmol) in dichloromethane (1 ml) was added rhodium (II) acetate dimer (20 mg, 0.05 mmol). To the mixture was added dropwise at room temperature over 4 h a solution of ethyl diazoacetate (0.43 ml, 0.47 g, 4.15 mmol) in dichloromethane (2.5 ml). The mixture was stirred at room temperature for 60 h. The mixture was purified by silica column (40 g) chromatography eluting with 1:1 hexane:dichloromethane then dichloromethane. Product-containing fractions were purified further by silica column (10 g) chromatography eluting with 9:1 hexane:dichloromethane then dichloromethane. Product-containing fractions were combined and concentrated in vacuo to give the title compound as a colourless oil (75 mg, 8%).

Workup

  1. customThe mixture was purified by silica column (40 g) chromatography
  2. washeluting with 1:1 hexane
  3. customProduct-containing fractions were purified further by silica column (10 g) chromatography
  4. washeluting with 9:1 hexane
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6b77db97f79e4f38a7bdb5f81f84bbbf
Source dataset
uspto-grants-2006_05
Patent number
US07049444B2

Reaction notes

Loading…