Cesium carbonate → HCID 71571903, compound

HRID 532194Notes

Reaction equation

HRID 532194 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4](B2OC(C)(C)C(C)(C)O2)[CH:5]=[C:6]([F:9])[C:7]=1[Cl:8].Br[C:20]([C:22]([F:25])([F:24])[F:23])=[CH2:21].C([O-])([O-])=O.[Cs+].[Cs+].[OH:32][N:33]=[C:34](Cl)[C:35]1[CH:46]=[CH:45][C:38]2[B:39]([OH:44])[O:40][C:41]([CH3:43])([CH3:42])[C:37]=2[CH:36]=1>C1COCC1.CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]([C:20]2([C:22]([F:25])([F:24])[F:23])[O:32][N:33]=[C:34]([C:35]3[CH:46]=[CH:45][C:38]4[B:39]([OH:44])[O:40][C:41]([CH3:43])([CH3:42])[C:37]=4[CH:36]=3)[CH2:21]2)[CH:5]=[C:6]([F:9])[C:7]=1[Cl:8]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 2726961-Propene, 2-bromo-3,3,3-trifluoro-HCID 86685046N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chlorideHCID 89572650HCID 89572650, compound

Product 1

HCID 71571903HCID 71571903, compoundYield 12%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 2-(3,4-dichloro-5-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.5 g, 1.73 mmol), 2-bromo-3,3,3-trifluoroprop-1-ene (0.38 g, 2.16 mmol), Cs2CO3 (1.8 mL, 2M, 3.6 mmol) and Pd(PPh3)2Cl2 (38 mg) in THF (10 mL) was heated at 70° C. in a sealed tube for 4 h. The mixture was cooled to rt, and then N,1-dihydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbimidoyl chloride (345 mg, 1.44 mmol) in DMF (20 mL) at rt and TEA (0.6 mL, 4.32 mmol) were added. The reaction mixture was stirred for 12 h, poured into ice-water and extracted with EA. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column eluted with PE-EA (10:1 to 3:1) and then purified by prep-TLC to give 80 mg of the title compound as a white solid (yield 10%). 1H NMR (400 MHz, DMSO-d6): δ 9.23 (s, 1 H), 7.77-7.69 (m, 5 H), 4.44 (d, J=18.8 Hz, 1 H), 4.32 (d, J=18.8 Hz, 1 H), 1.47 (s, 6 H) ppm; MS: m/z=462 (M+1, ESI+).

Workup

  1. temperatureThe mixture was cooled to rt
  2. extractionextracted with EA
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column
  8. washeluted with PE-EA (10:1 to 3:1)
  9. custompurified by prep-TLC

Sources & evidence

ORD record
ord-2d820a708ec74fccb3c7ffbf324f309e
Source dataset
uspto-grants-2014_10
Patent number
US08853186B2

Reaction notes

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