1,2-Dimethoxyethane → 9-(5-Bromo-2-ethylphenyl)-3-oxaspiro[5.5]undecane-8,10-dione

HRID 537683

Reaction equation

HRID 537683 reaction equation
[IH2+].[CH2:2]([C:4]1[CH:9]=[CH:8][C:7]([Br:10])=[CH:6][C:5]=1B(O)O)[CH3:3].[OH2:14].[OH-:15].[Li+].CO[CH2:19][CH2:20][O:21][CH3:22]>O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:10][C:7]1[CH:8]=[CH:9][C:4]([CH2:2][CH3:3])=[C:5]([CH:7]2[C:8](=[O:14])[CH2:9][C:4]3([CH2:19][CH2:20][O:21][CH2:22][CH2:2]3)[CH2:5][C:6]2=[O:15])[CH:6]=1

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 168937Lithium hydroxide, monohydrateHCID 3715291Iodine, ion (I1+)HCID 594459412-Ethyl-5-bromophenylboronic acid

Product 1

HCID 666799999-(5-Bromo-2-ethylphenyl)-3-oxaspiro[5.5]undecane-8,10-dione

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

A portion of the iodonium ylide (2.0 g, 5.21 mmol) is added to a mixture of 2-ethyl-5-bromophenylboronic acid (1.43 g, 6.25 mmol), palladium(II) acetate (59 mg, 0.26 mmol) and lithium hydroxide monohydrate (0.656 g, 15.6 mmol) in 1,2-dimethoxyethane (40 ml) and water (10 ml), and the mixture is heated at 50° C. for 6 hours, and then allowed to stand at room temperature overnight. The mixture is filtered through diatomaceous earth, washing the filter cake with water (50 ml) and ethyl acetate (50 ml). The organic phase is discarded. The aqueous phase is acidified to pH2 by addition of concentrated hydrochloric acid, and then extracted with ethyl acetate. The organic extract is dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give 9-(5-bromo-2-ethylphenyl)-3-oxaspiro[5.5]undecane-8,10-dione.

Workup

  1. filtrationThe mixture is filtered through diatomaceous earth
  2. washwashing the filter cake with water (50 ml) and ethyl acetate (50 ml)
  3. additionThe aqueous phase is acidified to pH2 by addition of concentrated hydrochloric acid
  4. extractionextracted with ethyl acetate
  5. extractionThe organic extract
  6. dry with materialis dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customthe filtrate is evaporated under reduced pressure
  9. customThe residue is purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-145deb73b74741cb952ea9c9df55a26f
Source dataset
uspto-grants-2014_10
Patent number
US08865623B2

Linked notes

Loading…