Cesium carbonate → HCID 59447605, compound

HRID 1518417Notes

Reaction equation

HRID 1518417 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[S:7]1[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[N:9]=[C:8]1[N:16]([CH2:43][O:44][CH2:45][CH2:46][Si:47]([CH3:50])([CH3:49])[CH3:48])[C:17]([C:19]1[CH:20]=[CH:21][CH:22]=[C:23]2[C:28]=1[CH2:27][N:26]([C:29]1[N:34]=[C:33]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C:32](Br)=[CH:31][CH:30]=1)[CH2:25][CH2:24]2)=[O:18].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.[CH2:85]([O:88][C:89]1[CH:94]=[CH:93][CH:92]=[CH:91][CH:90]=1)[C:86]#[CH:87]>CC#N.CC#N.Cl[Pd]Cl>[S:7]1[C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[N:9]=[C:8]1[N:16]([CH2:43][O:44][CH2:45][CH2:46][Si:47]([CH3:50])([CH3:49])[CH3:48])[C:17]([C:19]1[CH:20]=[CH:21][CH:22]=[C:23]2[C:28]=1[CH2:27][N:26]([C:29]1[N:34]=[C:33]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C:32]([C:87]#[C:86][CH2:85][O:88][C:89]3[CH:94]=[CH:93][CH:92]=[CH:91][CH:90]=3)=[CH:31][CH:30]=1)[CH2:25][CH2:24]2)=[O:18]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 83613(Prop-2-ynyloxy)benzeneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 59447604HCID 59447604, compound

Product 1

HCID 59447605HCID 59447605, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalyst

Conditions

Temperature
105 °C

Procedure

To pre-dried Cs2CO3 (378 mg, 1.16 mmol) was added compound 121C (180 mg, 0.26 mmol), 2-dicyclohexylphosphino-2′,4′,6′-tri-iso-propyl-1,1′-biphenyl (18 mg, 0.04 mmol) and bis(acetonitrile)dichloropalladium(II) (3.2 mg, 0.012 mmol). The atmosphere was purged with nitrogen and following the addition of propionitrile (3.0 mL) the mixture was stirred at room temperature for 10 min. before phenyl propargyl ether (205 mg, 1.54 mmol) was added. The mixture was heated at 105° C. for 1 hr, cooled to room temperature, concentrated, diluted with saturated NH4Cl and extracted with EtOAc (3×). The organic phases were washed with brine (1×), dried (Na2SO4), filtered, and concentrated. The crude material was purified by flash column chromatography on silica gel using a gradient of PE:EtOAc 100:0-85:15, to give the product (90 mg, 47%): 1H NMR (300 MHz, CDCl3) δ 8.28 (d, 1H), 7.69 (d, 1H), 7.57 (m, 2H), 7.47 (t, 1H), 7.38-7.26 (m, 5H), 6.99 (m, 3H), 6.82 (d, 1H), 5.98 (s, 2H), 5.24 (s, 2H), 4.92 (s, 2H), 4.07 (t, 2H), 3.74 (t, 2H), 1.60 (s, 9H), 0.97 (t, 2H), −0.09 (s, 9H).

Workup

  1. customThe atmosphere was purged with nitrogen
  2. additionthe addition of propionitrile (3.0 mL) the mixture
  3. additionwas added
  4. temperaturecooled to room temperature
  5. concentrationconcentrated
  6. additiondiluted with saturated NH4Cl
  7. extractionextracted with EtOAc (3×)
  8. washThe organic phases were washed with brine (1×)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude material was purified by flash column chromatography on silica gel using a gradient of PE

Sources & evidence

ORD record
ord-8050d25804b8400886fcd8ca5244d090
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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