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

HRID 1974775Notes

Reaction equation

HRID 1974775 reaction equation
[OH:1][CH:2]1[C:9](=[CH2:10])[CH2:8][C@H:7]2[C@@H:3]1[CH2:4][C@@H:5]([O:27][Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[C@H:6]2/[CH:11]=[CH:12]/[C@@H:13]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[O:35]1[CH:40]=[CH:39][CH2:38][CH2:37][CH2:36]1.O>C(Cl)Cl.C1C=CC(N=NC2C=CC(N)=NC=2N)=CC=1.Cl.CC1C=CC(S(O)(=O)=O)=CC=1>[O:35]1[CH2:36][CH2:37][CH2:38][CH2:39][CH:40]1[O:1][CH:2]1[C:9](=[CH2:10])[CH2:8][C@H:7]2[C@@H:3]1[CH2:4][C@@:5]([C:3]([CH3:7])([CH3:4])[CH3:2])([O:27][Si:28]([C:31]([CH3:33])([CH3:32])[CH3:34])([CH3:29])[CH3:30])[C@H:6]2/[CH:11]=[CH:12]/[C@@H:13]([O:19][Si:20]([C:23]([CH3:24])([CH3:25])[CH3:26])([CH3:21])[CH3:22])[CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

Participants

6

Reactant 3

HCID 962WaterHCID 80803,4-dihydro-2H-pyranHCID 13955240(1S,2RS,5S,6S,7R)-2-hydroxy-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane

Product 1

HCID 22850338(1S,2RS,5S,6S,7R)-2-(2-tetrahydropyranyloxy)-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyl-7-t-butyldimethylsilyloxybicyclo[3.3.0]octaneYield 176%

Reagents, catalysts & solvents 2

HCID 21909214Pyridium p-toluenesulfonateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

(1S,2RS,5S,6S,7R)-2-hydroxy-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane (127 mg, 0.25 mmole) obained in Example 3 was dissolved in 2 ml of methylene chloride. Dihydropyrane (42 mg, 0.50 mmole) and pyridium p-toluenesulfonate (5 mg) were added to the solution, and the mixture was stirred at room temperature for 8 hours. Water and methylene chloride were added to the reaction mixture to perform extraction. The resulting organic layer was washed with an aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated. The resulting crude product was subjected to column chromatography (silica gel 15 g, hexane/ethyl acetate=30/1) to give (1S,2RS,5S,6S,7R)-2-(2-tetrahydropyranyloxy)-3-methylene-6-[(E,3S)-3-t-butyldimethylsilyloxy-1-octenyl]-7-t-butyl-7-t-butyldimethylsilyloxybicyclo[3.3.0]octane (130 mg, 0.22 mmole, 88%).

Workup

  1. extractionextraction
  2. washThe resulting organic layer was washed with an aqueous solution of sodium chloride
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-d3f358db81d94d6ebdf9cee7a1fbc034
Source dataset
uspto-grants-1994_02
Patent number
US05283349

Reaction notes

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