Cesium carbonate → HCID 58677612, compound

HRID 1012640Notes

Reaction equation

HRID 1012640 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[C:14]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=3)[CH:13]=[CH:12][C:11]=2[CH3:26])=[O:9])=[C:4]([N+:27]([O-:29])=[O:28])[CH:3]=1.[F:30][C:31]1[CH:37]=[CH:36][C:34]([NH2:35])=[C:33]([CH3:38])[CH:32]=1.C([O-])([O-])=O.[Cs+].[Cs+].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>O1CCOCC1.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].O>[F:30][C:31]1[CH:37]=[CH:36][C:34]([NH:35][C:2]2[CH:7]=[CH:6][C:5]([C:8]([C:10]3[CH:15]=[C:14]([O:16][CH2:17][C:18]4[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=4)[CH:13]=[CH:12][C:11]=3[CH3:26])=[O:9])=[C:4]([N+:27]([O-:29])=[O:28])[CH:3]=2)=[C:33]([CH3:38])[CH:32]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 679824-Fluoro-2-methylanilineHCID 634876Binap, (A+-)-HCID 67314788HCID 67314788, compound

Product 1

HCID 58677612HCID 58677612, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Compound 504 (0.6 g, 1.35 mmol) was dissolved in 1,4-dioxan (15 mL). 4-Fluoro-2-methylaniline (0.22 mL, 2.0 mmol), Cs2CO3 (0.61 g, 1.88 mmol), BINAP (0.06 g, 0.1 mmol) and Pd2(dba)3 (0.031 g, 0.03 mmol) were added and the reaction mixture was stirred under an argon atmosphere at 100° C. for 18 h. H2O was added and the water phase was extracted with EtOAc (×2). The combined organic phases were washed with brine, dried (MgSO4), filtered and concentrated in vacuo. The crude product was purified by flash chromatography using a gradient of EtOAc/petroleum ether (40-60) 0:100→30:70. This afforded the title compound. 1H NMR (CDCl3) δ 7.32 (d, 1H), 7.30-7.14 (m, 4H), 7.11 (d, 1H), 7.06-6.91 (m, 3H), 6.88 (m, 2H), 6.84-6.77 (m, 2H), 5.87 (bs, 1H), 4.88 (s, 2H), 3.80 (s, 3H), 2.49 (s, 3H), 2.25 (s, 3H).

Workup

  1. extractionthe water phase was extracted with EtOAc (×2)
  2. washThe combined organic phases were washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-4e76586dd7c84a3ebac8b0bc6d57bc39
Source dataset
uspto-grants-2011_07
Patent number
US07977387B2

Reaction notes

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