Cesium carbonate → HCID 18506862, compound

HRID 1355476Notes

Reaction equation

HRID 1355476 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][N:13]=1)[C:5]([N:7]([O:9][CH3:10])[CH3:8])=[O:6].C([O-])([O-])=O.[Cs+].[Cs+].[CH3:20][C:21]1(C)[C:47]2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=C[C:22]1=2.C([NH:66][C:67](=[O:69])[O-:68])(C)(C)C>O1CCOCC1.O.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]>[CH3:10][O:9][N:7]([CH3:8])[C:5]([C:4]1[CH:11]=[CH:12][N:13]=[C:2]([NH:66][C:67](=[O:69])[O:68][C:21]([CH3:47])([CH3:22])[CH3:20])[CH:3]=1)=[O:6]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 185068942-Chloro-N-methoxy-N-methylisonicotinamideHCID 21252905Tert-butylcarbamate

Product 1

HCID 18506862HCID 18506862, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 2-chloro-N-methoxy-N-methylisonicotinamide (16-1, 500 mg, 2.49 mmole) in dry dioxane (5 ml) was added Cs2CO3 (1.22 g, 3.74 mmole), Xanthphos (216 mg, 0.37 mmole (Kranenburg, M. et. al. Organometallics 1995, 14, 3081-3089)), Pd2(dba)3 (114 mg, 0.12 mmole), and tert-butylcarbamate (350 mg, 2.99 mmole) then the mixture was heated to reflux. After 18 hr the mixture was cooled to RT., diluted with H2O, and extracted with EtOAc (3×). The combined organic layers were dried (MgSO4), filtered, and concentrated. Flash column chromatography (50% EtOAc/hexanes) gave the titled compound as a pale yellow solid. 1H-NMR (500 MHz, CDCl3) δ8.31 (d, 1H, J=5.13 Hz), 8.16 (bs, 1H), 7.74 (s, 1H), 7.12 (d, 1H, J=5.13 Hz), 3.61 (s, 3H), 3.34 (s, 3H), 1.53 (s, 9H); MS (ES) (M+H)+282.

Workup

  1. temperaturethe mixture was heated to reflux
  2. extractionextracted with EtOAc (3×)
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-0baa6f478b3d43c69bafa5f9e56b8299
Source dataset
uspto-grants-2003_07
Patent number
US06586423B2

Reaction notes

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