3-(Tributylstannyl)pyridine → 4-[(4-Methoxy-3-methylphenyl)(oxo)acetyl]-2-pyridin-3-ylbenzonitrile

HRID 643475Notes

Reaction equation

HRID 643475 reaction equation
Br[C:2]1[CH:9]=[C:8]([C:10](=[O:22])[C:11]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[C:15]([CH3:21])[CH:14]=2)=[O:12])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].C([Sn](CCCC)(CCCC)[C:28]1[CH:29]=[N:30][CH:31]=[CH:32][CH:33]=1)CCC>C(OCCOCC)C.CC1C=CC=CC=1[P](C1C=CC=CC=1C)([Pd](Cl)(Cl)[P](C1=C(C)C=CC=C1)(C1C=CC=CC=1C)C1C=CC=CC=1C)C1C=CC=CC=1C>[CH3:20][O:19][C:16]1[CH:17]=[CH:18][C:13]([C:11](=[O:12])[C:10]([C:8]2[CH:7]=[CH:6][C:3]([C:4]#[N:5])=[C:2]([C:28]3[CH:29]=[N:30][CH:31]=[CH:32][CH:33]=3)[CH:9]=2)=[O:22])=[CH:14][C:15]=1[CH3:21]

Participants

5

Reactant 2

HCID 34838483-(Tributylstannyl)pyridineHCID 686800872-Bromo-4-[(4-methoxy-3-methylphenyl)(oxo)acetyl]benzonitrile

Product 1

HCID 461800374-[(4-Methoxy-3-methylphenyl)(oxo)acetyl]-2-pyridin-3-ylbenzonitrileYield 91%

Reagents, catalysts & solvents 2

HCID 178424406HCID 178424406, compoundCatalystHCID 12375Ethylene glycol diethyl etherSolvent

Conditions

Temperature
145 °C

Procedure

A mixture of 2-bromo-4-[(4-methoxy-3-methylphenyl)(oxo)acetyl]benzonitrile (200 mg, 0.56 mmol) and 3-(tributylstannyl)pyridine (268 mg, 0.73 mmol) in 1,2-diethoxyethane is treated with dichlorobis(tri-o-tolylphosphine)palladium(II) (39.6 mg, 0.05 mmol), heated at 145° C., stirred for 30 min. and filtered to remove the catalyst. The filtrate is evaporated to dryness. The resultant residue is purified by flash chromatography (SiO2, 2/1 hexanes/EtOAc as eluent) and crystallization from ethyl ether/hexanes to afford the title compound as a yellow solid, 181 mg (91% yield), identified by HNMR and mass spectral analyses. MS m/e 357 (M+H)+; 1H NMR (400 MHz, DMSO-d6) δ 2.21 (s, 3H), 3.93 (s, 3H), 7.18 (d, J=8.69 Hz, 1H), 7.61 (m, 1H), 7.82 (d, J=8.54, 1H), 7.84 (dd, J=8.54, 1.99 Hz 1 H), 8.07 (dd, J=7.76, 1.67 Hz, 1H), 8.12 (m, J=1.38 Hz, 2H), 8.25 (d, J=8.08 Hz, 1H), 8.74 (m, 1H), 8.85 (d, 1.68 Hz, 1H).

Workup

  1. filtrationfiltered
  2. customto remove the catalyst
  3. customThe filtrate is evaporated to dryness
  4. customThe resultant residue is purified by flash chromatography (SiO2, 2/1 hexanes/EtOAc as eluent) and crystallization from ethyl ether/hexanes

Sources & evidence

ORD record
ord-c45526e4d88b47d494c9a462a7ae5780
Source dataset
uspto-grants-2010_04
Patent number
US07700602B2

Reaction notes

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