Chloride → HCID 71114876, compound

HRID 1624029Notes

Reaction equation

HRID 1624029 reaction equation
[Cl-].[C:2]([C:4]1[CH:9]=[CH:8][C:7](B(O)O)=[CH:6][CH:5]=1)#[N:3].[CH3:13][C:14]1([CH3:20])[C:18](=[O:19])[CH:17]=[CH:16][CH2:15]1.C(=O)([O-])[O-].[K+].[K+]>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(OCC)(=O)C.C(O)(C)C.O1CCCC1>[CH3:13][C:14]1([CH3:20])[C:18](=[O:19])[CH2:17][CH:16]([C:7]2[CH:8]=[CH:9][C:4]([C:2]#[N:3])=[CH:5][CH:6]=2)[CH2:15]1

Participants

9

Reactant 4

HCID 312ChlorideHCID 11430Potassium CarbonateHCID 27343264-Cyanophenylboronic acidHCID 110733712-Cyclopenten-1-one, 5,5-dimethyl-

Product 1

HCID 71114876HCID 71114876, compoundYield 88.2%

Reagents, catalysts & solvents 4

HCID 634876Binap, (A+-)-CatalystHCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Bis(1,5-cyclooctadienerhodium chloride) (1.09 g, 2.18 mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (3.05 g, 4.90 mmol) are added to tetrahydrofuran (72 mL) and the mixture is stirred under a nitrogen atmosphere for 30 minutes. This solution is added to a mixture of 4-cyanophenylboronic acid (80.04 g, 544.68 mmol), 5,5-dimethylcyclopent-2-en-1-one (24 g, 217.87 mmol), potassium carbonate (40.65 g, 294.13 mmol), tetrahydrofuran (144 mL), and isopropyl alcohol (16.7 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 (500 mL) and is extracted with ethyl acetate (2×500 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 6:1 hexane:ethyl acetate to give the title compound (41 g, 88%, 192.24 mmol). 1H NMR (300.13 MHz, CDCl3) δ 7.65-7.62 (m, 2H), 7.37 (d, J=8.1 Hz, 2H), 3.56-3.43 (m, 1H), 2.86-2.76 (m, 1H), 2.42-2.32 (m, 1H), 2.32-2.24 (m, 1H), 1.86 (t, J=12.4 Hz, 1H), 1.17 (s, 3H), 1.15 (s, 3H).

Workup

  1. stirringThe mixture is stirred at 60° C. for 16 hours
  2. concentrationconcentrated to dryness
  3. additionThe crude mixture is poured into water (500 mL)
  4. extractionis extracted with ethyl acetate (2×500 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 6:1 hexane

Sources & evidence

ORD record
ord-79e962d3c35e4785b04384173d9faef6
Source dataset
uspto-grants-2014_07
Patent number
US08778984B2

Reaction notes

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