Cesium carbonate → HCID 68787459, compound

HRID 1632042Notes

Reaction equation

HRID 1632042 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].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.[NH2:63][C:64]1[CH:65]=[CH:66][C:67]([O:79][CH3:80])=[C:68]([C:70]2[CH:75]=[CH:74][CH:73]=[C:72]([C:76](=[O:78])[CH3:77])[CH:71]=2)[CH:69]=1>C1(C)C=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]>[CH3:80][O:79][C:67]1[CH:66]=[CH:65][C:64]([NH:63][C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)=[CH:69][C:68]=1[C:70]1[CH:75]=[CH:74][CH:73]=[C:72]([C:76](=[O:78])[CH3:77])[CH:71]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 124951-Iodo-4-nitrobenzeneHCID 634876Binap, (A+-)-HCID 58020323HCID 58020323, compound

Product 1

HCID 68787459HCID 68787459, compoundYield 23%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

To a 40 mL vial equipped with a stir bar was placed 1-iodo-4-nitrobenzene (1.26 g, 5.07 mmol), cesium carbonate (2.20 g, 6.76 mmol), (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (316 mg, 0.507 mmol), and a solution of (5′-amino-2′-methoxy-biphenyl-3-yl)-ethanone (I-47, Y═H, Z═NH2, R1═CH3, R2═COCH3) synthesized above (816 mg, 3.38 mmol) in toluene (13.5 mL). The mixture was stirred for 10 minutes and then tris(dibenzylideneacetone)dipalladium(0) (310 mg, 0.338 mmol) and the mixture was heated to 110° C. for 16 hours. The reaction was cooled to room temperature and then filtered through Celite. The filtrate was treated with water (40 mL), 1M HCl (40 mL) and then Extracted with ethyl acetate (2×75 mL). The organic portions were combined, washed with brine (75 mL), dried (MgSO4) and concentrated. The crude material was purified by column chromatography utilizing 35% EtOAc/hexanes as the eluent to produce 277 mg of 1-[2′-methoxy-5′-(4-nitro-phenylamino)-biphenyl-3-yl]-ethanone (I-49, Y═H, Q=NH, R1═CH3, R2═COCH3, R3═NO2) as a dark orange solid in 23% yield.

Workup

  1. customTo a 40 mL vial equipped with a stir bar
  2. filtrationfiltered through Celite
  3. additionThe filtrate was treated with water (40 mL), 1M HCl (40 mL)
  4. extractionExtracted with ethyl acetate (2×75 mL)
  5. washwashed with brine (75 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customThe crude material was purified by column chromatography

Sources & evidence

ORD record
ord-d1c67f4972e943219a672c0291613f5a
Source dataset
uspto-grants-2014_07
Patent number
US08791267B2

Reaction notes

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