Chlorotrimethylsilane → HCID 18419719, compound

HRID 990091Notes

Reaction equation

HRID 990091 reaction equation
[CH:1]([Mg]Br)=[CH2:2].[C:5]1([C:11]2[C:12](=[O:17])[O:13][CH2:14][CH2:15][CH:16]=2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.Cl[Si](C)(C)C>O1CCCC1.[Cu]I>[C:5]1([CH:11]2[CH:16]([CH:1]=[CH2:2])[CH2:15][CH2:14][O:13][C:12]2=[O:17])[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 184196755,6-Dihydro-3-phenyl-2H-pyran-2-oneHCID 178418507HCID 178418507, compound

Product 1

HCID 18419719HCID 18419719, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

Vinylmagnesium bromide (77 ml, 1M THF) was added to a slurry of copper (I) iodide (7.37 g) in tetrahydrofuran (80 ml) at −78° C. under a nitrogen atmosphere. This mixture was stirred at −40° C. for 30 minutes, then recooled to −78° C. A solution of 3-phenyl-5,6-dihydro-2-pyrone (J. Org. Chem. 1967, 32, 2354) (4.6 g) and chlorotrimethylsilane (3.28 ml) in THF (80 ml) was added to the stirred mixture. Thin layer chromatography showed all starting material had reacted. The mixture was quenched with ammonium chloride (saturated aqueous solution) at −78° C. and the resulting mixture was allowed to come to room temperature and was stirred for 2 hours until the aqueous layer became dark blue. The mixture was filtered through Celite™ to remove any insoluble inorganics and the solution was extracted with ethyl acetate (3×100 ml). The pooled organic extracts were washed with brine, dried (MgSO4) and concentrated to give a yellow oil. This was purified on silica using 30-40% ether in hexane as eluant to afford the title compound (4.9 g, crystallised on standing) as a mixture of cis and trans isomers (2:1). Recrystallisation of this mixture from ether-hexane afforded the pure cis isomer as white prisms.

Workup

  1. customrecooled to −78° C
  2. customhad reacted
  3. customThe mixture was quenched with ammonium chloride (saturated aqueous solution) at −78° C.
  4. customto come to room temperature
  5. stirringwas stirred for 2 hours until the aqueous layer
  6. filtrationThe mixture was filtered through Celite™
  7. customto remove any insoluble inorganics
  8. extractionthe solution was extracted with ethyl acetate (3×100 ml)
  9. washThe pooled organic extracts were washed with brine
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated
  12. customto give a yellow oil
  13. customThis was purified on silica using 30-40% ether in hexane as eluant

Sources & evidence

ORD record
ord-7b1138bb8ff141f199e993a143c92237
Source dataset
uspto-grants-2002_10
Patent number
US06458830B1

Reaction notes

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