Potassium Carbonate → 4-(2-Methyl-5-oxo-1-cyclopenten-1-yl)benzonitrile

HRID 560053

Reaction equation

HRID 560053 reaction equation
Br[C:2]1[C:3](=[O:8])[CH2:4][CH2:5][C:6]=1[CH3:7].C([O-])([O-])=O.[K+].[K+].[C:15]([C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1)#[N:16].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.CCO.[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:7][C:6]1[CH2:5][CH2:4][C:3](=[O:8])[C:2]=1[C:20]1[CH:21]=[CH:22][C:17]([C:15]#[N:16])=[CH:18][CH:19]=1

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 27343264-Cyanophenylboronic acidHCID 44370092-Bromo-3-methyl-2-cyclopenten-1-one

Product 1

HCID 219861594-(2-Methyl-5-oxo-1-cyclopenten-1-yl)benzonitrile

Reagents, catalysts & solvents 4

HCID 1542701,5-Diphenylpenta-1,4-dien-3-one;palladiumCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

2-Bromo-3-methyl-cyclopent-2-enone (Intermediate TEN1) (commercially available from Aldrich) (2.04 g, 11.4 mmol) and K2CO3 (3.16 g in 11 mL H2O) in toluene (45 mL) was treated with a solution 4-cyanophenylboronic acid (commercially available from Aldrich) (2.2 g, 15 mmol) in EtOH (27 mL). Tetrakis(triphenylphosphine) palladium(0) Pd(PPh3)4 (0.4 g), bis(dibenzylideneacetone) palladium(0), Pd2(dba)3 (0.055 g, ˜5 mol %) and triphenylphosphine (0.4 g) were added and the mixture was purged with N2 for 15 m. The mixture was heated to 80° C. for 15 h. The mixture was diluted with water and EtOAc:hexane. After extracting with EtOAc:hexane, the combined organic layers were dried over MgSO4, filtered and evaporated to dryness. The crude oil was purified by column chromatography on silica gel with CH2Cl2 to give 4-(2-methyl-5-oxo-cyclopent-1-enyl)-benzonitrile (Intermediate TEN2) 1.74 g.

Workup

  1. customthe mixture was purged with N2 for 15 m
  2. additionThe mixture was diluted with water and EtOAc
  3. extractionAfter extracting with EtOAc
  4. dry with materialhexane, the combined organic layers were dried over MgSO4
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe crude oil was purified by column chromatography on silica gel with CH2Cl2

Sources & evidence

ORD record
ord-0835510b88e74f8f87f08ae99a818abd
Source dataset
uspto-grants-2011_11
Patent number
US08063087B2

Linked notes

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