Chloride → HCID 71114821, compound

HRID 1624038Notes

Reaction equation

HRID 1624038 reaction equation
[Cl-].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:48]([C:50]1[CH:55]=[CH:54][C:53](B(O)O)=[CH:52][CH:51]=1)#[N:49].[CH3:59][CH:60]1[C:65](=[O:66])[CH:64]=[CH:63][CH2:62][CH2:61]1.C(=O)([O-])[O-].[K+].[K+]>C(O)(C)C.O1CCCC1>[CH3:59][C@H:60]1[CH2:61][CH2:62][C@H:63]([C:53]2[CH:54]=[CH:55][C:50]([C:48]#[N:49])=[CH:51][CH:52]=2)[CH2:64][C:65]1=[O:66].[CH3:59][C@@H:60]1[CH2:61][CH2:62][C@H:63]([C:53]2[CH:54]=[CH:55][C:50]([C:48]#[N:49])=[CH:51][CH:52]=2)[CH2:64][C:65]1=[O:66]

Participants

9

Reactant 5

HCID 312ChlorideHCID 11430Potassium CarbonateHCID 634876Binap, (A+-)-HCID 27343264-Cyanophenylboronic acidHCID 110623356-Methylcyclohex-2-en-1-one

Product 2

HCID 71114821HCID 71114821, compoundYield 22%HCID 71114860HCID 71114860, compoundYield 22%

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

Bis(1,5-cyclooctadienerhodium chloride) (0.06 g, 0.12 mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.18 g, 0.29 mmol) are added to tetrahydrofuran (40 mL) and the mixture is stirred under a nitrogen atmosphere for 30 minutes. This solution is added to a mixture of 4-cyanophenylboronic acid (2.31 g, 15.69 mmol), 6-methylcyclohex-2-en-1-one (Journal of Organic Chemistry, 1980 45(10), 1852-1863) (1.28 g, 11.62 mmol), potassium carbonate (2.19 g, 15.69 mmol), and isopropyl alcohol (1.1 mL) at 60° C. The mixture is stirred at 60° C. for 16 hours and then concentrated to dryness. The crude mixture is poured into water (10 mL) and is extracted with ethyl acetate (2×20 mL). The organic extracts are dried over MgSO4, filtered through silica gel, and concentrated to dryness. The residue is purified by silica gel flash chromatography, eluting with 20% EtOAc/hexane to give (trans)-4-(4-methyl-3-oxo-cyclohexyl)benzonitrile (0.55 g, 22%) as the first eluting isomer and (cis)-4-(4-methyl-3-oxo-cyclohexyl)benzonitrile (0.55 g, 22%) as the second eluting isomer. ES/MS m/z 214 (M+H).

Workup

  1. stirringThe mixture is stirred at 60° C. for 16 hours
  2. concentrationconcentrated to dryness
  3. additionThe crude mixture is poured into water (10 mL)
  4. extractionis extracted with ethyl acetate (2×20 mL)
  5. dry with materialThe organic extracts are dried over MgSO4
  6. filtrationfiltered through silica gel
  7. concentrationconcentrated to dryness
  8. customThe residue is purified by silica gel flash chromatography
  9. washeluting with 20% EtOAc/hexane

Sources & evidence

ORD record
ord-99b75ae895b44da9a2d5ed4e60ed4922
Source dataset
uspto-grants-2014_07
Patent number
US08778984B2

Reaction notes

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