Dimethyl Sulfoxide → 3-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]tetrahydro-4-methoxy-5-methyl-2H-pyran-2-carboxaldehyde

HRID 326775Notes

Reaction equation

HRID 326775 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH3:11][C:12]([Si:15]([CH3:29])([CH3:28])[O:16][CH:17]1[CH:22]([O:23][CH3:24])[CH:21]([CH3:25])[CH2:20][O:19][CH:18]1[CH2:26][OH:27])([CH3:14])[CH3:13].C(N(CC)CC)C>ClCCl>[CH3:11][C:12]([Si:15]([CH3:29])([CH3:28])[O:16][CH:17]1[CH:22]([O:23][CH3:24])[CH:21]([CH3:25])[CH2:20][O:19][CH:18]1[CH:26]=[O:27])([CH3:13])[CH3:14]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 196996953-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]tetrahydro-4-methoxy-5-methyl-2H-pyran-2-methanol

Product 1

HCID 196996923-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]tetrahydro-4-methoxy-5-methyl-2H-pyran-2-carboxaldehydeYield 87.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Into a stirred solution of oxalylchloride (0.07 ml, 0.81 mmol) in dry dichloromethane (3 ml) was dropped a solution of dry dimethylsulfoxide (0.11 ml, 1.49 mmol) in dry dichloromethane at -60° C. and stirring was continued at this temperature (-60° C.) for 15 minutes. Then a solution of the title compound of Example 39 (180 mg, 0.62 mmol) in dry dichloromethane (1 ml) was added slowly. After being stirred for additional 15 minutes at -60° C. triethylamine (0.43 ml, 3.1 mmol) was added slowly, the mixture was stirred for 10 minutes at -60° C. and then allowed to come to ambient temperature and stirred for 40 minutes at this temperature. The solvent was removed on a rotary evaporator, and the residue was partitionated between ether and ice-water. The organic phase was separated, dried over sodium sulfate and evaporated in vacuo to leave an oil (157 mg) which was chromatographed on silica gel eluting with ethyl acetate/petroleum ether (1:4). The relevant fractions were combined and then evaporated in vacuo to yield the desired title aldehyde as a pale yellowish oil. Yield 108 mg.

Workup

  1. additionwas added slowly
  2. stirringthe mixture was stirred for 10 minutes at -60° C.
  3. customto come to ambient temperature
  4. stirringstirred for 40 minutes at this temperature
  5. customThe solvent was removed on a rotary evaporator
  6. customThe organic phase was separated
  7. dry with materialdried over sodium sulfate
  8. customevaporated in vacuo

Sources & evidence

ORD record
ord-83f5b497e4ce4789a00ef81a0ee4d66e
Source dataset
uspto-grants-1993_12
Patent number
US05270334

Reaction notes

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