Phosphonium, [2-(1,3-dioxolan-2-yl)ethyl]triphenyl-, bromide (1:1) → (1S,3aS,7aR)-1-acetoxymethyl-5-((Z)-2-(1,3-dioxolan-2-yl)ethyliden]-7a-methylperhydroinden-3a-ol

HRID 725179Notes

Reaction equation

HRID 725179 reaction equation
[Br-].[O:2]1[CH2:6][CH2:5][O:4][CH:3]1[CH2:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.[C:33]([O:36][CH2:37][C@@H:38]1[C@:46]2([CH3:47])[C@@:41]([OH:49])([CH2:42][C:43](=O)[CH2:44][CH2:45]2)[CH2:40][CH2:39]1)(=[O:35])[CH3:34]>C1COCC1.CCCCCC.O>[C:33]([O:36][CH2:37][C@@H:38]1[C@:46]2([CH3:47])[C@@:41]([OH:49])([CH2:42]/[C:43](=[CH:8]\[CH2:7][CH:3]3[O:2][CH2:6][CH2:5][O:4]3)/[CH2:44][CH2:45]2)[CH2:40][CH2:39]1)(=[O:35])[CH3:34].[C:33]([O:36][CH2:37][C@@H:38]1[C@:46]2([CH3:47])[C@@:41]([OH:49])([CH2:42]/[C:43](=[CH:8]/[CH2:7][CH:3]3[O:2][CH2:6][CH2:5][O:4]3)/[CH2:44][CH2:45]2)[CH2:40][CH2:39]1)(=[O:35])[CH3:34]

Participants

8

Reactant 3

HCID 2733834Phosphonium, [2-(1,3-dioxolan-2-yl)ethyl]triphenyl-, bromide (1:1)HCID 22880912(1S,3aS,7aR)-1-acetoxymethyl-3a-hydroxy-7a-methyl-5-perhydroindenoneHCID 178418339Butyllithium

Product 2

HCID 70050966(1S,3aS,7aR)-1-acetoxymethyl-5-((Z)-2-(1,3-dioxolan-2-yl)ethyliden]-7a-methylperhydroinden-3a-olHCID 70051762(1S,3aS,7aR)-1-acetoxymethyl-5-[(E)-2-(1,3-dioxolan-2-yl)ethyliden]-7a-methylperhydroinden-3a-ol

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-25 °C

Procedure

To a suspension of 26.0 g of [2-(1,3-dioxolan-2-yl)ethyl]-triphenylphosphonium bromide in 300 ml of anhydrous THF, cooled at -25° C., 36 ml of 1.6N n-butyllithium in n-hexane were added, under a nitrogen atmosphere. After stirring for 1 hr, a solution of 5.0 g of (1S,3aS,7aR)-1-acetoxymethyl-3a-hydroxy-7a-methyl-5-perhydroindenone in 50 ml of anhydrous THF was added and the resulting mixture was stirred at -20° C. for 4 hrs, then at room temperature per 3 hrs. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and evaporated to dryness under reduced pressure. The residue was purified by flash-chromatography (SiO2) with methylene chloride/acetone 95:5 as the eluant to give 1.88 g of (1S,3aS,7aR)-1-acetoxymethyl-5-[(Z)-2-(1,3-dioxolan-2-yl)ethyliden]-7a-methyl-perhydroinden-3a-ol and 1.46 g of (1S,3aS,7aR)-1-acetoxymethyl-5-[(E)-2-(1,3-dioxolan-2-yl)ethyliden]-7a-methylperhydroinden-3a-ol as pale yellow oils.

Workup

  1. stirringthe resulting mixture was stirred at -20° C. for 4 hrs
  2. waitat room temperature per 3 hrs
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was purified by flash-chromatography (SiO2) with methylene chloride/acetone 95:5 as the eluant

Sources & evidence

ORD record
ord-2ef608b08de543708326784058f4167f
Source dataset
uspto-grants-1998_01
Patent number
US05705531

Reaction notes

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