Pyridine → [(1-Allylcyclohexyl)oxy](tert-butyl)dimethylsilane

HRID 44721Notes

Reaction equation

HRID 44721 reaction equation
N1C=CC=CC=1.[Si:7](Cl)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8].[CH2:15]([C:18]1([OH:24])[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1)[CH:16]=[CH2:17].O([Si](C(C)(C)C)(C)C)S(C(F)(F)F)(=O)=O>CN(C)C1C=CN=CC=1.C(#N)C>[CH2:15]([C:18]1([O:24][Si:7]([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8])[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1)[CH:16]=[CH2:17]

Participants

7

Reactant 4

HCID 1049PyridineHCID 28928tert-Butyldimethylsilyl chlorideHCID 791451-Allyl-1-cyclohexanolHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonate2×

Product 1

HCID 57457814[(1-Allylcyclohexyl)oxy](tert-butyl)dimethylsilaneYield 97.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

Pyridine (11.7 mL, 145 mmol), 4-dimethylaminopyridine (DMAP, 0.59 g, 4.82 mmol) and tert-butyldimethylsilyl chloride (8.71 g, 57.8 mmol) were added to a solution of 1-allylcyclohexanol (48.2 mmol) in acetonitrile (120 mL). The reaction was heated at reflux overnight, then cooled to rt and concentrated to about 50 mL under reduced pressure. The solution was cooled to 0° C. and tert-butyldimethylsilyl triflate (13.3 mL, 57.8 mmol) was added. After the solution had stirred overnight at rt, additional tert-butyldimethylsilyl triflate (5.00 mL) was added and the solution was stirred for 6 h longer. The reaction was quenched with saturated aqueous sodium bicarbonate (120 mL) and extracted with dichloromethane (100 mL, then 2×75 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated to give a colorless oil that was purified on a on a HORIZON High-Performance Flash Chromatography (HPFC) instrument (available from Biotage, Inc, Charlottesville, Va., USA) (silica gel, gradient elution with 0-5% ethyl acetate/hexanes) to afford [(1-allylcyclohexyl)oxy](tert-butyl)dimethylsilane as a colorless oil (11.96 g, 97%).

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux overnight
  3. concentrationconcentrated to about 50 mL under reduced pressure
  4. temperatureThe solution was cooled to 0° C.
  5. stirringthe solution was stirred for 6 h longer
  6. customThe reaction was quenched with saturated aqueous sodium bicarbonate (120 mL)
  7. extractionextracted with dichloromethane (100 mL
  8. dry with materialThe combined organic layers were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto give a colorless oil that
  12. customwas purified on a
  13. washon a HORIZON High-Performance Flash Chromatography (HPFC) instrument (available from Biotage, Inc, Charlottesville, Va., USA) (silica gel, gradient elution with 0-5% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-6ec100e0efd74e1694633bfdebf25bc8
Source dataset
uspto-grants-2013_09
Patent number
US08541438B2

Reaction notes

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