6-Carbomethoxymethyl-6-ethyl-2-cyclohexen-1-one → HCID 23324905, compound

HRID 1380928Notes

Reaction equation

HRID 1380928 reaction equation
[CH:1]1([Mg]Br)[CH2:5][CH2:4][CH2:3][CH2:2]1.[C:8]([CH2:12][C:13]1([CH2:20][CH3:21])[C:18](=[O:19])[CH:17]=[CH:16][CH2:15][CH2:14]1)([O:10][CH3:11])=[O:9]>C1COCC1.S(C)C>[C:8]([CH2:12][C:13]1([CH2:20][CH3:21])[CH2:14][CH2:15][CH:16]([CH:1]2[CH2:5][CH2:4][CH2:3][CH2:2]2)[CH2:17][C:18]1=[O:19])([O:10][CH3:11])=[O:9]

Participants

5

Reactant 2

HCID 136492416-Carbomethoxymethyl-6-ethyl-2-cyclohexen-1-oneHCID 178419650HCID 178419650, compound

Product 1

HCID 23324905HCID 23324905, compoundYield 74%

Reagents, catalysts & solvents 2

HCID 1068Dimethyl SulfideSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

Following the procedure of Paquette et al., J. Am. Chem. Soc., 103, 1831 (1981) a solution of cyclopentylmagnesium bromide (222.5 mmol, 111.2 ml of 2M in Et2O), in 481 ml of dry THF under nitrogen was cooled to -78° C. and treated dropwise with a solution of 120.4 mmol (24.75 g) of CuBr.Me2S in 170 ml of Me2S. After 1.5 hours at -78° C., a solution of the enone, 6-carbomethoxymethyl-6-ethyl-2-cyclohexene-1-one prepared in Example 1, Step (c), (40.77 mmol, 8 g) in 80 ml of THF was added dropwise. After 1.5 hours, TLC indicated the consumption of enone and the reaction was quenched with 250 ml of 1M HCl (aq.) and extracted with 2×100 ml of CH2Cl2 and 2×100 ml of petroleum ether. Drying (Na2SO4) and flash chromatography afforded 8.027 g (30.13 mmol, 74%) of pale yellow oil containing a mixture of diastereomers. This material was combined with another batch to give 11.04 g and this was separated by preparative HPLC to afford 2.96 g of a less polar isomer and 4.3 g of a more polar isomer.

Workup

  1. waitAfter 1.5 hours
  2. customthe consumption of enone
  3. customthe reaction was quenched with 250 ml of 1M HCl (aq.)
  4. extractionextracted with 2×100 ml of CH2Cl2 and 2×100 ml of petroleum ether
  5. dry with materialDrying (Na2SO4) and flash chromatography

Sources & evidence

ORD record
ord-981db2a2a0bd4d8898d842c29f3295ec
Source dataset
uspto-grants-1986_04
Patent number
US04584312

Reaction notes

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