(3aS,6S,6aS)-6-(tert-butyldimethylsilyloxy)tetrahydrofuro[3,2-b]furan-3(2H)-one → tert-butyldimethyl((3R,3aS,6aR)-6-methylene hexahydrofuro[3,2-b]furan-3-yloxy)silane

HRID 1887392Notes

Reaction equation

HRID 1887392 reaction equation
[CH3:1]C(C)([O-])C.[K+].[Si:7]([O:14][C@@H:15]1[C@H:19]2[O:20][CH2:21][C:22](=O)[C@H:18]2[O:17][CH2:16]1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1.O>[C:10]([Si:7]([CH3:8])([CH3:9])[O:14][C@@H:15]1[CH2:16][O:17][C@@H:18]2[C:22](=[CH2:1])[CH2:21][O:20][C@H:19]12)([CH3:11])([CH3:12])[CH3:13]

Participants

6

Reactant 2

HCID 15834481(3aS,6S,6aS)-6-(tert-butyldimethylsilyloxy)tetrahydrofuro[3,2-b]furan-3(2H)-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 67049508tert-butyldimethyl((3R,3aS,6aR)-6-methylene hexahydrofuro[3,2-b]furan-3-yloxy)silaneYield 234.7%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A stirred suspension of methyltriphenylphosphonium bromide (1.84 g, 5.16 mmol) and potassium tert-butoxide (578 mg, 5.16 mmol) in tetrahydrofuran (15 mL) was heated at reflux under an atmosphere of argon for 3 hours then allowed to cool to ambient temperature. A solution of ketone (87) (888 mg, 3.44 mmol) in tetrahydrofuran (7.5 mL) was added then heating at reflux continued for 2.25 hours. The mixture was diluted with water (30 mL) then the product extracted into diethyl ether (2×30 mL). The combined organic layers were washed with brine (25 mL), dried (MgSO4), filtered and reduced in vacuo to leave residue (2.07 g). Flash chromatography over silica, eluting with ethyl acetate:heptane mixtures 0:100 to 15:85 gave alkene (88) as a colourless oil (799 mg, 91%).

Workup

  1. temperaturewas heated
  2. temperatureat reflux under an atmosphere of argon for 3 hours
  3. temperaturethen heating
  4. temperatureat reflux
  5. extractionthe product extracted into diethyl ether (2×30 mL)
  6. washThe combined organic layers were washed with brine (25 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered

Sources & evidence

ORD record
ord-83399376f7214be481204cf2bd7a6324
Source dataset
uspto-grants-2013_08
Patent number
US08501744B2

Reaction notes

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