Cesium carbonate → HCID 90152010, compound

HRID 1506791Notes

Reaction equation

HRID 1506791 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:9]=[C:10]3[C:15](=[CH:16][CH:17]=2)[C:14](=[O:18])[C:13]([CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])([CH3:19])[CH2:12][CH2:11]3)=[N:6][CH:7]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:33]1[CH:34]=[CH:35][C:36]([C:39]([F:42])([F:41])[F:40])=[N:37][CH:38]=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].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:19][C:13]1([CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH2:12][CH2:11][C:10]2[C:15](=[CH:16][CH:17]=[C:8]([C:5]3[CH:4]=[CH:3][C:2]([NH:1][C:33]4[CH:38]=[N:37][C:36]([C:39]([F:42])([F:41])[F:40])=[CH:35][CH:34]=4)=[CH:7][N:6]=3)[CH:9]=2)[C:14]1=[O:18]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 27611975-Bromo-2-(trifluoromethyl)pyridineHCID 90135712HCID 90135712, compound

Product 1

HCID 90152010HCID 90152010, compoundYield 56%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Pd2(dba)3 (0.068 g, 0.074 mmol) and BINAP (0.046 g, 0.074 mmol) were added to a solution of 3G (0.5 g, 1.478 mmol) in 10 mL of toluene under argon atmosphere, followed by cesium carbonate (1.44 g, 4.43 mmol) and 5-bromo-2-(trifluoromethyl)pyridine (0.334 g, 1.478 mmol). The mixture was degassed for 10 min. The reaction mixture was stirred at 100° C. for 6 h and allowed to warm to room temperature. The reaction mixture was diluted with ethyl acetate and water. The separated organic layer was dried over sodium sulfate and filtered, and the filtrate was concentrated. The crude product was purified by flash chromatography using 8% ethyl acetate in hexane to afford the title compound 3H (0.4 g, 53%) as a solid. 1H NMR (300 MHz, DMSO-d6): δ 9.34 (s, 1H), 8.60 (d, J=2.7 Hz, 1H), 8.51 (d, J=2.2 Hz, 1H), 8.08-7.91 (m, 4H), 7.88-7.63 (m, 3H), 4.01 (q, J=7.1 Hz, 2H), 3.08 (m, 2H), 2.85 (d, J=15.9 Hz, 1H), 2.50-2.29 (m, 2H), 1.93 (m, 1H), 1.19 (s, 3H), 1.13 (t, J=6.9 Hz, 3H). ESI-MS m/z: 484 (M+H)+.

Workup

  1. customThe mixture was degassed for 10 min
  2. temperatureto warm to room temperature
  3. additionThe reaction mixture was diluted with ethyl acetate and water
  4. dry with materialThe separated organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-011658ad4bea46568181a05e311c6974
Source dataset
uspto-grants-2015_12
Patent number
US09221766B2

Reaction notes

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