Chlorotrimethylsilane → HCID 89499939, compound

HRID 1527842Notes

Reaction equation

HRID 1527842 reaction equation
[C:1]1([CH2:7][CH2:8][CH:9]=[CH2:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:11][C:12]1[CH2:17][CH2:16][CH2:15][C:14](=[O:18])[CH:13]=1.C[Si](Cl)(C)C>C(Cl)Cl.CCOCC>[CH3:11][C:12]1([CH2:10][CH2:9][CH2:8][CH2:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:17]=[CH:16][CH2:15][C:14](=[O:18])[CH2:13]1

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 130333-ButenylbenzeneHCID 145113-Methyl-2-cyclohexen-1-one

Product 1

HCID 89499939HCID 89499939, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

Cp2ZrHCl (103 mg, 0.40 mmol, 2.0 eq.) was added to a stirred, room temperature, solution of 4-phenyl-1-butene (0.08 mL, 0.5 mmol, 2.5 eq.) in CH2Cl2 (0.40 mL) under an argon atmosphere. After stirring for about 20 min, the resulting clear yellow solution was transferred via syringe over about 1 min to a clear colourless stirred solution of CuOTf-ligand complex (15.0 mg, 0.020 mmol, 0.10 eq.) in Et2O (2.0 mL) under an argon atmosphere. The resulting dark mixture was allowed to stir for an additional 10 min before 3-methyl-2-cyclohexenone (0.023 mL, 0.20 mmol, 1.0 eq.) and then TMSCl (0.13 mL, 1.0 mmol, 5.0 eq.) were added dropwise via syringe. The reaction was stirred until complete (TLC control (EtOAc/Petrol 1:9)). The reaction was quenched by the addition of Et2O (ca 3 mL) and then NH4Cl (1 M. aq., ca 1.5 mL). The mixture was partitioned between water and Et2O and the aqueous phase extracted with Et2O (3×10 mL). The combined organic phase was washed with NaHCO3 (aq. sat., ca 10 mL), dried (Na2SO4), filtered and concentrated in vacuo to give an oil. Flash column chromatography of the residue (EtOAc/petrol; SiO2) gave (−)-3-methyl-3-(4-phenylbutyl)cyclohexenone (21.9 mg, 0.09 mmol, 45%) as a yellow oil. HPLC analysis indicated an enantiomeric excess of 60% [Chiralpak® IA; flow 1 ml/min; hexane/i-PrOH: 99:1; λ=210 nm; minor enantiomer (+)-3-methyl-3-(4-phenylbutyl)cyclohexenone, tR=14.90 min; major enantiomer (−)-3-methyl-3-(4-phenylbutyl)cyclohexenone, tR=15.70 min].

Workup

  1. customThe reaction was quenched by the addition of Et2O (ca 3 mL)
  2. customThe mixture was partitioned between water and Et2O
  3. extractionthe aqueous phase extracted with Et2O (3×10 mL)
  4. washThe combined organic phase was washed with NaHCO3 (aq. sat., ca 10 mL)
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give an oil

Sources & evidence

ORD record
ord-95f8765da4ac4f62b74e3517e991c70d
Source dataset
uspto-grants-2015_07
Patent number
US09090545B2

Reaction notes

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