Triacetoxyperiodinane → 9-cis-4-Oxoretinoic acid

HRID 1369043Notes

Reaction equation

HRID 1369043 reaction equation
[CH3:1][C:2]1[CH:7]([OH:8])[CH2:6][CH2:5][C:4]([CH3:10])([CH3:9])[C:3]=1/[CH:11]=[CH:12]/[C:13](/[CH3:23])=[CH:14]\[CH:15]=[CH:16]\[C:17](\[CH3:22])=[CH:18]\[C:19]([OH:21])=[O:20].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.C([O-])(O)=O.[Na+]>C(Cl)Cl.CCOCC>[CH3:1][C:2]1[C:7](=[O:8])[CH2:6][CH2:5][C:4]([CH3:9])([CH3:10])[C:3]=1/[CH:11]=[CH:12]/[C:13](/[CH3:23])=[CH:14]\[CH:15]=[CH:16]\[C:17](\[CH3:22])=[CH:18]\[C:19]([OH:21])=[O:20]

Participants

6

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 20849244HCID 20849244, compound

Product 1

HCID 99729399-cis-4-Oxoretinoic acidYield 90%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 4-hydroxy-9-cis-retinoic acid (16 mg, 0.05 mmole) in CH2Cl2 (1.5 ml) was added Dess-Martin reagent [see Dess and Martin in J. Org. Chem. 48:4155 (1983)] (42 mg, 0.1 mmole) in one portion at 25° C. After stirring for 5 minutes, the mixture was diluted with 10 ml of ether and to this was added saturated aqueous NaHCO3 (5 ml) containing Na2 SO3 (55 mg). The mixture was stirred for 20 minutes to dissolve the solid and the layers separated. The ether layer was washed with H2O (2×5 ml), brine (5 ml) and dried (MgSO4). The solvent was recovered under reduced pressure and residue was subjected to flash column chromatography (silica, 60% ether in Hexane) to give 4-keto-9-cis-retinoic acid (14 mg. 90%), characterized as follows: TLC rf=0.6 (silica, 80% ether in hexane);1HNMR (400 mHz, CDCl3) δ7.05 (dd, J=16, 12 Hz, 1H, olefinic), 6.82 (d, J=16 Hz, 1 H, olefinic), 6.32 (d, J=16 Hz, 1H, olefinic), 6.30 (d, J=16 Hz, 1H, olefinic), 6.20 (d, J=12 Hz, 1H, olefinic), 5.80 (s, 1H, olefinic), 2.5 (t, J=7 Hz, 2H, CH2—CO), 2.31 (s, 3H, CH3), 2.01 (s, 3H, CH3), 1.9 (s, 3H, CH3), 1.89 (m, 2H, CH2), 1.20 (s, 6H, 2×CH3).

Workup

  1. additioncontaining Na2 SO3 (55 mg)
  2. stirringThe mixture was stirred for 20 minutes
  3. dissolutionto dissolve the solid
  4. customthe layers separated
  5. washThe ether layer was washed with H2O (2×5 ml), brine (5 ml)
  6. dry with materialdried (MgSO4)
  7. customThe solvent was recovered under reduced pressure and residue

Sources & evidence

ORD record
ord-0d831dc5ea2147d7a2cd997b7123f254
Source dataset
uspto-grants-2003_06
Patent number
US06576676B1

Reaction notes

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