Diiodomethane → HCID 66817825, compound

HRID 1755060Notes

Reaction equation

HRID 1755060 reaction equation
[Zn](CC)[CH2:2]C.[CH2:6]([O:13][C:14]([CH:16]1[CH2:21][CH2:20][C:19](=[CH2:22])[CH2:18][CH2:17]1)=[O:15])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(I)I>C1(C)C=CC=CC=1>[CH2:6]([O:13][C:14]([CH:16]1[CH2:21][CH2:20][C:19]2([CH2:2][CH2:22]2)[CH2:18][CH2:17]1)=[O:15])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 6346Diiodomethane3×HCID 66817244HCID 66817244, compoundHCID 178418750HCID 178418750, compound3×

Product 1

HCID 66817825HCID 66817825, compoundYield 77.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Et2Zn (1.08 M solution in hexane, 5.23 ml, 5.65 mmol) was added to a solution of 4-methylene-cyclohexanecarboxylic acid benzyl ester (86.3 mg, 375 μmol) in toluene (1.4 ml), and the mixture was stirred at room temperature for 30 minutes. CH2I2 (500 μl, 6.22 mmol) was added to the reaction mixture at 0° C., and the mixture was stirred at 60° C. for 28 hours. Thereafter, Et2Zn (1.08 M solution in hexane, 2.60 ml, 2.22 mmol) and CH2I2 (260 μl, 3.23 mmol) were added to the reaction mixture, and the mixture was stirred at 60° C. for four days. Further, Et2Zn (1.08 M solution in hexane, 2.60 ml, 2.22 mmol) and CH2I2 (500 μl, 6.22 mmol) were added to the reaction mixture, and the mixture was stirred at 60° C. for one day. The reaction mixture was quenched by adding a 1% aqueous HCl solution and diluted with ethyl acetate and Et2O. The organic layer was then washed with a 1% aqueous HCl solution, a saturated aqueous sodium bicarbonate solution and saturated brine, and then dried over MgSO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→65/35) to give spiro[2.5]octane-6-carboxylic acid benzyl ester (70.6 mg, 77%).

Workup

  1. stirringthe mixture was stirred at 60° C. for 28 hours
  2. stirringthe mixture was stirred at 60° C. for four days
  3. stirringthe mixture was stirred at 60° C. for one day
  4. customThe reaction mixture was quenched
  5. additionby adding a 1% aqueous HCl solution
  6. additiondiluted with ethyl acetate and Et2O
  7. washThe organic layer was then washed with a 1% aqueous HCl solution
  8. dry with materiala saturated aqueous sodium bicarbonate solution and saturated brine, and then dried over MgSO4
  9. concentrationconcentrated under reduced pressure
  10. customThe resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→65/35)

Sources & evidence

ORD record
ord-8f701b555122414085d784e91716481f
Source dataset
uspto-grants-2015_10
Patent number
US09169254B2

Reaction notes

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