Dimethyl Sulfoxide → HCID 11833079, compound

HRID 863166Notes

Reaction equation

HRID 863166 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Si:11]([O:18][C@@H:19]1[C@@H:24]([O:25][CH3:26])[C@@H:23]([CH3:27])[CH2:22][O:21][C@H:20]1[CH2:28][OH:29])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCl.C(Cl)Cl>[Si:11]([O:18][C@@H:19]1[C@@H:24]([O:25][CH3:26])[C@@H:23]([CH3:27])[CH2:22][O:21][C@H:20]1[CH:28]=[O:29])([C:14]([CH3:16])([CH3:17])[CH3:15])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10891600HCID 10891600, compound

Product 1

HCID 11833079HCID 11833079, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 24526ChlorineSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of oxalyl chloride (0.036 ml, 0.42 mmole) in dry CH2 Cl2 (0.5 ml) there was added dropwise a solution of dry DMSO (0.049 ml, 0.69 mmole) in dry CH2Cl2 (0.1 ml) at -78° C. over 5 min. After stirring for 10 min at -78° C., a solution of (2S,3R,4S,5S)-[3-(tert-butyldimethylsilyloxy)-4-methoxy-5-methyltetrahydro-2H-pyran-2-yl]methanol (0.1 g, 0.345 mmole) in dry CH2Cl2 (0.1 ml) was added dropwise to the resulting milky suspension over 5 min at -78° C. After stirring for 15 min at -78° C., triethylamine (0.24 ml, 1.73 mmole) was added dropwise to the reaction mixture over 3 min, and stirring was continued for 30 min at -78° C. The reaction mixture was then warmed up to room temperature gradually and partitioned between CH2Cl2 (10 ml) and water (10 ml). The methylene chloride layer was washed with brine (5 ml×2), dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The residue was chromatographed on silica gel using AcOEt/n-hexane (1:9) as an eluent to give (2R,3R,4S,5S)-3-(tert-butyldimethylsilyloxy)-4-methoxy-5-methyltetrahydro-2H-pyran-2-carbaldehyde (0.085 g, 86% yield) as a colorless oil; EI-MS: m/z 288 (M+); 1H-NMR (CDCl3)d: 0.85 (3H,d,J=7 Hz), 0.87 (9H,s), 2.28 (1H,m), 3.12 (1H,dd,J=4 & 5 Hz), 3.28 (3H,s), 3.59 (1H,dd,J=5 & 11.5 Hz), 3.81 (1H,d,J=4. Hz), 3.81 (1H,dd,J=9 & 11.5 Hz), 4.08 (1H,dd,J=4 & 5 Hz), 9.80 (1H,s).

Workup

  1. stirringAfter stirring for 15 min at -78° C.
  2. stirringstirring
  3. waitwas continued for 30 min at -78° C
  4. temperatureThe reaction mixture was then warmed up to room temperature gradually
  5. custompartitioned between CH2Cl2 (10 ml) and water (10 ml)
  6. washThe methylene chloride layer was washed with brine (5 ml×2)
  7. dry with materialdried over anhydrous sodium sulfate
  8. customevaporated to dryness under reduced pressure
  9. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-223e89351dc849a4877730110e28f9f2
Source dataset
uspto-grants-1998_02
Patent number
US05719291

Reaction notes

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