Hydrochloric Acid → methyl (2R,3R,4S,5S)-3-benzyloxy-4-methoxy-5-methyltetrahydro-2H-pyran-2-carboxylate

HRID 863168Notes

Reaction equation

HRID 863168 reaction equation
I([O-])(=O)(=O)=O.[Na+].[CH2:7]([O:14][C@@H:15]1[C@@H:20]([O:21][CH3:22])[C@@H:19]([CH3:23])[CH2:18][O:17][C@H:16]1[CH2:24][OH:25])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.Cl.C[Si](C=[N+]=[N-])(C)C.CCCCCC.[CH3:40][OH:41]>[Ru]=O.CCOCC.O.C(Cl)(Cl)(Cl)Cl.C(#N)C>[CH2:7]([O:14][C@@H:15]1[C@@H:20]([O:21][CH3:22])[C@@H:19]([CH3:23])[CH2:18][O:17][C@H:16]1[C:24]([O:41][CH3:40])=[O:25])[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

12

Reactant 6

HCID 313Hydrochloric AcidHCID 887MethanolHCID 8058HexaneHCID 167693TrimethylsilyldiazomethaneHCID 23667635Sodium periodateHCID 67672097(2S,3R,4S,5S)-(3-benzyloxy-4-methoxy-5-methyltetrahydro-2H-pyran-2-yl)methanol

Product 1

HCID 57058836methyl (2R,3R,4S,5S)-3-benzyloxy-4-methoxy-5-methyltetrahydro-2H-pyran-2-carboxylateYield 30%

Reagents, catalysts & solvents 5

HCID 178527103HCID 178527103, compoundCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolventHCID 6342AcetonitrileSolvent

Procedure

Sodium periodate (0.05 g, 0.234 mmole) and ruthenium oxide (0.02 g, 0.15 mmole) were added to a vigorously stirred emulsion of (2S,3R,4S,5S)-(3-benzyloxy-4-methoxy-5-methyltetrahydro-2H-pyran-2-yl)methanol (0.02 g, 0.075 mmole) in a mixed solvent of acetonitrile (2 ml), carbon tetrachloride (2 ml) and water (3 ml). After stirring for 12 hr, the reaction mixture was adjusted to pH 2 with 0.1N aqueous HCl and partitioned between ether (20 ml) and water (10 ml). The ether layer was dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. To a solution of the resulting crude acid in a mixed solvent of ether (5 ml) and MeOH (1 ml) there was added a 10% solution of trimethylsilyldiazomethane in n-hexane (0.5 g, 0.44 mmole). The mixture was stirred at room temperature for 10 min. The solution was evaporated to dryness under reduced pressure. The residue was chromatographed on silica gel using AcOEt/n-hexane (2:8) as an eluent to give methyl (2R,3R,4S,5S)-3-benzyloxy-4-methoxy-5-methyltetrahydro-2H-pyran-2-carboxylate (6.6 mg, 30% yield) as an oil; EI-MS m/z 294 (M+); 1H-NMR (CDCl3)d: 1.0 (3H,d,J=7.2 Hz), 2.2 (1H,m), 3.20 (1H,dd,J=5 & 11 Hz), 3.35 (1H,dd,J=4 & 9 Hz), 3.6 (1H,t,J=9 Hz), 3.65 (3H, s), 3.7 (3H,s), 3.8 (1H,d,J=9 Hz), 4.0 (1H, dd,J=4 & 11 Hz), 4.59 (1H,d,J=12 Hz), 4.62 (1H,d,J=12 Hz), 7.3 (5H,m).

Workup

  1. custompartitioned between ether (20 ml) and water (10 ml)
  2. dry with materialThe ether layer was dried over anhydrous magnesium sulfate
  3. customevaporated to dryness under reduced pressure
  4. stirringThe mixture was stirred at room temperature for 10 min
  5. customThe solution was evaporated to dryness under reduced pressure
  6. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-b0a3a471054048d1aa98984a51ebd45f
Source dataset
uspto-grants-1998_02
Patent number
US05719291

Reaction notes

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