Sodium hydride → HCID 22855995, compound

HRID 863170Notes

Reaction equation

HRID 863170 reaction equation
[I-].[CH3:2][S+](C)(C)=O.[H-].[Na+].[CH3:9][O:10][C@H:11]1[C@@H:16]([CH3:17])[CH2:15][O:14][C@@H:13](/[CH:18]=[CH:19]/[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[C:12]1=[O:27]>CNS(NC)(=O)=O.O1CCCC1>[CH3:9][O:10][C@@H:11]1[C@:12]2([O:27][CH2:2]2)[C@H:13](/[CH:18]=[CH:19]/[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[O:14][CH2:15][C@@H:16]1[CH3:17]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 67804486HCID 67804486, compound

Product 1

HCID 22855995HCID 22855995, compoundYield 72.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 89736N,N'-DimethylsulfamideSolvent

Procedure

Trimethylsulfoxonium iodide (74 mg) was added to a suspension of sodium hydride (14 mg, 60% oil suspension) in dry dimethylsulfamide (1 ml) . The mixture was stirred for 1 hr at room temperature. A solution of (2S,4S,5S)-4-methoxy-5-methyl-2-[(E)-1-nonenyl]tetrahydro-2H-pyran-3-one (30 mg) in dry tetrahydrofuran (0.2 ml) was added dropwise. After stirring for 2 hrs at room temperature, the reaction was quenched by addition of saturated aqueous ammonium chloride solution. The mixture was extracted with diethyl ether, and the combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated. Purification of the residue by preparative thin layer chromatography (n-hexane:ethyl acetate=10:1) gave (3S,4S,7S,8S)-8-methoxy-7-methyl-4-[(E)-1-nonenyl]-1,5-dioxaspiro[2,5]octane (23 mg, 72% yield) as colorless oil; EI-MS: m/z 282 (M+); 1 H-NMR (CDCl3)d: 0.87 (3H,t,J=7 Hz), 1.10 (1H,d,J=7 Hz), 1.2-1.4 (10H,m), 2.0 (2H,m), 2.2 (1H,m), 2.43 (1H,d,J=5 Hz), 2.80 (1H,d,J=5 Hz), 3.37 (3H,s), 3.52 (1H,d,J=3 Hz), 3.66 (1H,dd,J=3 & 12 Hz), 3.90 (1H,dd,J=4 & 12 Hz), 3.94 (1H,d,J=8 Hz), 5.56 (1H,dd,J=8 & 15 Hz), 5.71 (1H,m).

Workup

  1. stirringAfter stirring for 2 hrs at room temperature
  2. customthe reaction was quenched by addition of saturated aqueous ammonium chloride solution
  3. extractionThe mixture was extracted with diethyl ether
  4. washthe combined organic extracts were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification of the residue by preparative thin layer chromatography (n-hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-6f4fe6c19caa4d0a8d55a2eef09a67b8
Source dataset
uspto-grants-1998_02
Patent number
US05719291

Reaction notes

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