Quinone → Spiro[2.4]hept-5-ene-4,7diol Diacetate

HRID 1392932Notes

Reaction equation

HRID 1392932 reaction equation
[OH2:1].O.[C:3]([O-:6])(=[O:5])[CH3:4].[Li+].[Cl-].[Li+].[C:10]1(=[O:17])[CH:15]=CC(=O)C=C1.[CH2:18]1[C:20]2([CH:24]=[CH:23][CH:22]=[CH:21]2)[CH2:19]1>C(O)(=O)C.O.CCCCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[O-2].[Mn+4].[O-2]>[C:3]([O:6][CH:21]1[CH:22]=[CH:23][CH:24]([O:1][C:10](=[O:17])[CH3:15])[C:20]21[CH2:19][CH2:18]2)(=[O:5])[CH3:4]

Participants

10

Reactant 4

HCID 4650QuinoneHCID 136590Spiro(2,4)hepta-4,6-dieneHCID 433294Lithium ChlorideHCID 23666338Lithium acetate dihydrate

Product 1

HCID 131726807Spiro[2.4]hept-5-ene-4,7diol DiacetateYield 77.1%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 178418406HCID 178418406, compoundCatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8003PentaneSolvent

Procedure

To a two phase mixture of palladium acetate (1.7 g), lithium acetate dihydrate (123.6 g), lithium chloride (30.0 g), manganese (IV) oxide (15.3 g) and p-benzoquinone (1.4 g) in acetic acid (250 ml), water (420 ml) and pentane (3.7 l) was added spiro[2.4]hepta-4,6-diene (7.7 g) and the resulting mixture was stirred at ambient temperature for 24 hours. The reaction mixture was filtered through a celite plug washing with pentane (1 l). The organic phase was collected, washed successively with saturated sodium bicarbonate solution (500 ml), water (500 ml) and brine (100 ml) then concentrated to dryness under reduced pressure. The residue was absorbed onto silica and purified by chromatography (SiO2; 9:1 isohexane:ethyl acetate) to afford the subtitle compound (2.1 g).

Workup

  1. filtrationThe reaction mixture was filtered through a celite plug
  2. washwashing with pentane (1 l)
  3. customThe organic phase was collected
  4. washwashed successively with saturated sodium bicarbonate solution (500 ml), water (500 ml) and brine (100 ml)
  5. concentrationthen concentrated to dryness under reduced pressure
  6. customThe residue was absorbed onto silica
  7. custompurified by chromatography (SiO2; 9:1 isohexane:ethyl acetate)

Sources & evidence

ORD record
ord-0a22a7c1c0104482926a5b32dbb902d2
Source dataset
uspto-grants-2008_03
Patent number
US07345047B2

Reaction notes

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