Diethyl Ether → 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-1-(3-formyl-cyclopent-2-enyl)-2-methylpropan-1-ol

HRID 1274885Notes

Reaction equation

HRID 1274885 reaction equation
[CH:1]1([CH:7]([OH:25])[C:8]([N:11]2[C:16](=[O:17])[C:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[C:14]([CH3:24])[O:13][CH2:12]2)([CH3:10])[CH3:9])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.I([O-])(=O)(=O)=[O:27].[Na+].CCOCC>[Os](=O)(=O)(=O)=O.C1(C)C=CC=CC=1.O1CCCC1.O>[CH3:24][C:14]1[O:13][CH2:12][N:11]([C:8]([CH3:10])([CH3:9])[CH:7]([CH:1]2[CH2:2][CH2:3][C:4]([CH:5]=[O:27])=[CH:6]2)[OH:25])[C:16](=[O:17])[C:15]=1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

8

Reactant 3

HCID 3283Diethyl EtherHCID 221183281-(cyclohex-2-enyl)-2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropan-1-olHCID 23667635Sodium periodate

Product 1

HCID 221182872-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-1-(3-formyl-cyclopent-2-enyl)-2-methylpropan-1-olYield 7.7%

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Osmium tetroxide (3 drops of 5%) in toluene was added to a solution of 1-(cyclohex-2-enyl)-2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropan-1-ol (6.9 g) and sodium periodate (6.0 g) in a mixture of tetrahydrofuran and water at 20° C. After stirring for 5 hours, ether was added and the organic phase washed (brine), dried (magnesium sulphate) and evaporated. The residue was dissolved in ether, then sodium hydoxide (20% aqueous solution) added and the mixture stirred for 0.5 hour at 20° C. The organic phase was washed (brine), dried (magnesium sulphate), evaporated and the residue purified by silica gel column chromatography, eluting with n-hexane/ethyl acetate (1:1) to give 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-1-(3-formyl-cyclopent-2-enyl)-2-methylpropan-1-ol (0.55 g), NMR: 1.51(s,3H), 1.57(s,3H), 1.85(1H), 1.93(s,3H), 2.15(1H), 2.40(1H), 2.65(1H), 2.98(1H), 3.53(dd,1H), 5.21(d,1H), 5.35(d,3H), 5.49(d,1H), 6.92(s,1H), 7.25-7.43(5H), 9.74(s,1H).

Workup

  1. washthe organic phase washed (brine)
  2. dry with materialdried (magnesium sulphate)
  3. customevaporated
  4. dissolutionThe residue was dissolved in ether
  5. additionsodium hydoxide (20% aqueous solution) added
  6. stirringthe mixture stirred for 0.5 hour at 20° C
  7. washThe organic phase was washed (brine)
  8. dry with materialdried (magnesium sulphate)
  9. customevaporated
  10. customthe residue purified by silica gel column chromatography
  11. washeluting with n-hexane/ethyl acetate (1:1)

Sources & evidence

ORD record
ord-7fecce4ba95c410592473d770aaa497c
Source dataset
uspto-grants-2000_12
Patent number
US06159902

Reaction notes

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