Cesium carbonate → HCID 25095378, compound

HRID 913381Notes

Reaction equation

HRID 913381 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].Cl[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[C:14]#[C:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[C:22]([O:26][C:27]([N:29]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[NH2:30])=[O:28])([CH3:25])([CH3:24])[CH3:23]>Cl[Pd]Cl.CN(C=O)C>[C:22]([O:26][C:27](=[O:28])[N:29]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[N:30]1[C:8]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:14]=[C:15]1[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)([CH3:25])([CH3:23])[CH3:24]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 251161-Chloro-2-(phenylethynyl)benzeneHCID 11160087HCID 11160087, compound

Product 1

HCID 25095378HCID 25095378, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 24290Palladium ChlorideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

Following the general procedure outlined above, a reaction tube was charged with 4.4 mg PdCl2 (5 mol %), 14.5 mg tBu3PHBF4 (10 mol %), 228.1 mg Cs2CO3 (1.4 equiv.) and 2.5 mL DMF. After stirring for 30 min at RT under a flow of argon, 1-chloro-2-phenylethynyl-benzene (106.3 mg, 1.0 equiv.) and N-phenylhydrazine carboxylic acid tert-butyl ester (145.8 mg, 1.4 equiv.) were added and the reaction was heated to 110° C. for 3 hours. After cooling to RT, the reaction mixture was quenched with 30 mL NaHCO3 (saturated aqueous) and extracted with EtOAc (2×30 mL) and the organic phase was dried by eluting through a Varian Chem Elut 12198007 cartridge. Removal of the solvents afforded the crude N-aminoindole as a dark-brown oil that was purified by flash chromatography on silica using CH2Cl2/heptane to afford 164.8 mg (86%) of Phenyl-(2-phenyl-indol-1-yl)-carbamic acid tert-butyl ester as a yellowish oil. 1H-NMR (DMSO-d6) δ 1.25 (s, 9H), 6.85 (s, 1H), 7.10-7.14 (m, 3H), 7.15-7.18 (m, 1H), 7.23 (d, 2H, J=4.0 Hz), 7.26-7.30 (m, 2H), 7.39-7.41 (m, 1H), 7.44 (t, J=7.2 Hz, 2H), 7.52 (d, 2H, J=7.9 Hz), 7.65 (d, 1H, J=7.8 Hz); 13C-NMR (DMSO-d6) δ 27.3, 82.5, 101.4, 109.2, 120.8, 121.0, 123.1, 125.3, 125.7, 127.4, 128.4, 128.7, 128.8, 130.5, 136.7, 139.7, 140.9, 152.0; HRMS (FAB): Calculated for C25H25N2O2 (M+H+) 385.1916. found 385.1917.

Workup

  1. additionwere added
  2. temperatureAfter cooling to RT
  3. customthe reaction mixture was quenched with 30 mL NaHCO3 (saturated aqueous)
  4. extractionextracted with EtOAc (2×30 mL)
  5. customthe organic phase was dried
  6. washby eluting through a Varian Chem Elut 12198007 cartridge
  7. customRemoval of the solvents
  8. customafforded the crude N-aminoindole as a dark-brown oil that
  9. customwas purified by flash chromatography on silica

Sources & evidence

ORD record
ord-ad20dced61d442d297c525c3b1468572
Source dataset
uspto-grants-2011_09
Patent number
US08026375B2

Reaction notes

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