Cesium carbonate → HCID 59239861, compound

HRID 1851878Notes

Reaction equation

HRID 1851878 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])(=[O:16])[NH:14][NH2:15].C([O-])([O-])=O.[Cs+].[Cs+]>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].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].C1(C)C=CC=CC=1>[CH2:9]([O:8][C:6]([C:5]1[CH:11]=[CH:12][C:2]([N:14]([C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH2:15])=[CH:3][CH:4]=1)=[O:7])[CH3:10]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 22043Ethyl 4-bromobenzoateHCID 70091tert-Butyl carbazate

Product 1

HCID 59239861HCID 59239861, compound

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a 350 mL high-pressure vial was added ethyl 4-bromobenzoate (12.92 g, 56.4 mmol), t-butyl carbazate (14.91 g, 112.8 mmol), Pd2(dba)3 (0.516 g, 0.56 mmol), dppf (0.938 g, 1.69 mmol), Cs2CO3 (18.4 g, 56.4 mmol), and dry toluene (113 mL). The reaction mixture was degassed for 5 min, sealed and heated to 100° C. for 16 h. The completion of the reaction was monitored by analytical HPLC. The reaction mixture was allowed to cool to room temperature, diluted with DCM, filtered and the filtrate was concentrated. The crude was then purified by flash chromatography (AcOEt/Hexane (0→30%) to afford the desired product. ESI-MS (m/z): 265 [M+H—NH3]+, 225 [M+H-tBu]+, 181 [M+H-Boc]+. 1H NMR (400 MHz, DMSO-d6): δ (ppm) 1.31 (t, J=7.1 Hz, 3H, CH3 ethyl), 1.50 (s, 9H, CH3 Boc), 4.28 (q, J=7.1 Hz, 2H, CH2 ethyl), 5.14 (s, 2H, NH2), 7.70 (dt, J=8.8, 2.2 Hz, 2H, H2 and H6 phenyl), 7.87 (dt, J=8.8, 2.2 Hz, 2H, H3 and H5 phenyl).

Workup

  1. customThe reaction mixture was degassed for 5 min
  2. customsealed
  3. temperatureto cool to room temperature
  4. additiondiluted with DCM
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customThe crude was then purified by flash chromatography (AcOEt/Hexane (0→30%)

Sources & evidence

ORD record
ord-befe0bd12fdc48958d4140601ae66da7
Source dataset
uspto-grants-2015_02
Patent number
US08957093B2

Reaction notes

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