Cesium carbonate → HCID 131729806, compound

HRID 1511514Notes

Reaction equation

HRID 1511514 reaction equation
[C:1]([O:5][C:6](=[O:26])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][C:12](B2OC(C)(C)C(C)(C)O2)=[C:11]([O:24][CH3:25])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[C:27]([O:31][C:32](=[O:88])[CH2:33][N:34]([CH2:80][C:81]([O:83][C:84]([CH3:87])([CH3:86])[CH3:85])=[O:82])[CH2:35][C:36]1[CH:41]=[C:40](Br)[CH:39]=[C:38]([CH2:43][N:44]([CH2:71][CH2:72][C:73]2[CH:78]=[CH:77][C:76]([NH2:79])=[CH:75][CH:74]=2)[CH2:45][C:46]2[N:51]=[C:50]([CH2:52][N:53]([CH2:62][C:63]([O:65][C:66]([CH3:69])([CH3:68])[CH3:67])=[O:64])[CH2:54][C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[CH:49]=[C:48](Br)[CH:47]=2)[N:37]=1)([CH3:30])([CH3:29])[CH3:28].[C:89](=[O:92])([O-])[O-:90].[Cs+].[Cs+]>CN(C=O)C.O.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:27]([O:31][C:32](=[O:88])[CH2:33][N:34]([CH2:80][C:81]([O:83][C:84]([CH3:87])([CH3:86])[CH3:85])=[O:82])[CH2:35][C:36]1[CH:41]=[C:40]([C:14]2[CH:13]=[CH:12][C:11]([O:24][CH2:25][C:89]([O:90][C:1]([CH3:2])([CH3:4])[CH3:3])=[O:92])=[CH:10][C:9]=2[O:8][CH3:7])[CH:39]=[C:38]([CH2:43][N:44]([CH2:71][CH2:72][C:73]2[CH:78]=[CH:77][C:76]([NH2:79])=[CH:75][CH:74]=2)[CH2:45][C:46]2[N:51]=[C:50]([CH2:52][N:53]([CH2:62][C:63]([O:65][C:66]([CH3:69])([CH3:68])[CH3:67])=[O:64])[CH2:54][C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[CH:49]=[C:48]([C:12]3[CH:13]=[CH:14][C:9]([O:8][CH2:7][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:26])=[CH:10][C:11]=3[O:24][CH3:25])[CH:47]=2)[N:37]=1)([CH3:30])([CH3:29])[CH3:28]

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 87532850HCID 87532850, compoundHCID 131729805HCID 131729805, compound

Product 1

HCID 131729806HCID 131729806, compound

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Compound 3 (0.11 g, 0.30 mmol) and tetra(tert-butyl)-2,2′,2″,2′″-{[2-(4-aminophenyl)ethylimino]-bis(methylene)bis(4-bromopyridine-6,2-diyl)bis(methylenenitrilo)}tetrakis(acetate) (0.10 mg, 0.10 mmol) were dissolved in dry DMF (5 ml) and the mixture was deaerated with argon. Caesium carbonate (0.11 g, 0.34 mmol) and tetrakis(triphenylphosphine)palladium (4.6 mg, 0.004 mmol) were added to the mixture and the reaction was stirred overnight at 80° C. The reaction mixture was cooled to room temperature and diluted with water (10 ml) and ethyl acetate (10 ml). Black particles were removed by filtration through a pad of Celite. The organic layer was separated, washed with brine (20 ml) and dried over sodium sulphate. The product was purified by flash chromatography on silica gel (first 5% methanol in dichloromethane and finally 10%). The yield was 90.0 mg (69%). 1H NMR (CDCl3, 500 MHz): δ 7.63-7.72 (4H, m), 7.24 (2H, s), 6.90 (2H, d), 6.55 (2H, d), 6.50 (2H, d), 6.41 (2H, s), 4.42 (4H, s), 4.08 (4H, s), 3.96 (4H, s), 3.83 (6H, s), 3.53 (8H, s), 2.68-2.97 (4H, m), 1.45 (54H, m).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customBlack particles were removed by filtration through a pad of Celite
  3. customThe organic layer was separated
  4. washwashed with brine (20 ml)
  5. dry with materialdried over sodium sulphate
  6. customThe product was purified by flash chromatography on silica gel (first 5% methanol in dichloromethane and finally 10%)

Sources & evidence

ORD record
ord-820a852ed5a6478b97ca7b9f7492186e
Source dataset
uspto-grants-2012_07
Patent number
US08216856B2

Reaction notes

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