Naphthalene → (1S,2RS,5S,6S,7R)-2-hydroxy-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane

HRID 1974774Notes

Reaction equation

HRID 1974774 reaction equation
CS(O[CH2:6][C:7]12[O:39][CH:8]1[C@@H:9]1[C@H:13]([CH2:14]2)[C@H:12](/[CH:15]=[CH:16]/[C@@H:17]([O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[C@H:11]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[CH2:10]1)(=O)=O.C1C2C(=CC=CC=2)C=CC=1.[Na].[Cl-].[NH4+]>O1CCCC1.CCCCCC.C(OCC)(=O)C>[OH:39][CH:8]1[C:7](=[CH2:6])[CH2:14][C@H:13]2[C@@H:9]1[CH2:10][C@@H:11]([O:31][Si:32]([C:35]([CH3:36])([CH3:38])[CH3:37])([CH3:33])[CH3:34])[C@H:12]2/[CH:15]=[CH:16]/[C@@H:17]([O:23][Si:24]([C:27]([CH3:28])([CH3:29])[CH3:30])([CH3:25])[CH3:26])[CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]

Participants

7

Reactant 4

HCID 931NaphthaleneHCID 25517Ammonium Chloride2×HCID 5360545SodiumHCID 22850329(1S,2RS,-3RS,5S,6S,7R)-3-methanesulfonyloxymethyl-2,3-epoxy-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane

Product 1

HCID 13955240(1S,2RS,5S,6S,7R)-2-hydroxy-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octaneYield 78.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of 917 mg (1.52 mmoles) of (1S,2RS,-3RS,5S,6S,7R)-3-methanesulfonyloxymethyl-2,3-epoxy-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane obtained in Example 2 in 3 ml of tetrahydrofuran was added to an anion radical solution prepared by reacting naphthalene (1.28 g, 10 mmoles) with sodium (207 mg, 9 mmoles) in 30 ml of tetrahydrofuran at room temperature for I hour. The mixture was stirred at room temperature for 10 minutes and 3.0 g of ammonium chloride was added to the reaction solution. Then, a saturated aqueous solution of ammonium chloride was added and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give a crude product. It was subjected to column chromatography (silica gel 50 g; hexane/ethyl acetate=19/1) to give (1S,2RS,5S,-6S,7 R)-2-hydroxy-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy- 1-octenyl) -7-t-butyldimethylsilyloxybicyclo[3.3.0]octane (605 mg, 1.19 mmoles, 78%).

Workup

  1. customprepared
  2. customat room temperature
  3. extractionthe resulting mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with an aqueous solution of sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customto give a crude product

Sources & evidence

ORD record
ord-620689bb402e442caf16beae770c4586
Source dataset
uspto-grants-1994_02
Patent number
US05283349

Reaction notes

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