HCID 86684795, compound → HCID 86684797, compound

HRID 1527970Notes

Reaction equation

HRID 1527970 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[CH3:24])[CH2:9][C:10]([C:12]2[CH:17]=[CH:16][N:15]=[N:14][CH:13]=2)=[O:11])=[CH:4][CH:3]=1.[I-].[C:26]([O:30][C:31]([N:33]1[CH2:38][CH2:37][CH:36]([Zn+])[CH2:35][CH2:34]1)=[O:32])([CH3:29])([CH3:28])[CH3:27]>CN(C)C(=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[O:11]=[C:10]([C:12]1[CH:17]=[CH:16][N:15]=[N:14][CH:13]=1)[CH2:9][CH:8]([C:5]1[CH:4]=[CH:3][C:2]([CH:36]2[CH2:37][CH2:38][N:33]([C:31]([O:30][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:32])[CH2:34][CH2:35]2)=[CH:7][CH:6]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24]

Participants

6

Reactant 2

HCID 86684795HCID 86684795, compoundHCID 178452044HCID 178452044, compound

Product 1

HCID 86684797HCID 86684797, compoundYield 29%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst2×HCID 31374DimethylacetamideSolvent

Conditions

Temperature
85 °C

Procedure

To a yellow solution of 3-(4-bromophenyl)-1-(pyridazin-4-yl)-3-o-tolylpropan-1-one (example 2, step 3; 180 mg, 472 μmol) in N,N-dimethylacetamide (4 mL) were added copper(I) iodide (9 mg, 47 μmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (17.3 mg, 23.6 μmol) and (1-(tert-butoxycarbonyl)piperidin-4-yl)zinc(II) iodide solution (0.5 M in N,N-dimethylacetamide, 1.9 mL, 0.95 mmol; J. Org. Chem. 2004, 69, 5120). The reaction mixture was heated at 85° C., then after 5 h another portion of copper(I) iodide (9 mg, 47 μmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (17.3 mg, 23.6 μmol) was added, then after 1 h the reaction mixture was partitioned between sat, aq. ammonium chloride solution and ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and evaporated. The residue was suspended in ethyl acetate/heptane 1:1 and insoluble material was removed by filtration. The filtrate was purified by chromatography (SiO2; ethyl acetate/heptane 1:1) to produce the title compound (66 mg, 29%). Orange foam, MS: 486.4 [M+H]+.

Workup

  1. customafter 1 h the reaction mixture was partitioned
  2. washThe organic layer was washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customwas removed by filtration
  7. customThe filtrate was purified by chromatography (SiO2; ethyl acetate/heptane 1:1)

Sources & evidence

ORD record
ord-0b296b37ae9c4bd7813dadae67a96bcd
Source dataset
uspto-grants-2015_07
Patent number
US09090565B2

Reaction notes

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