Sodium Carbonate → HCID 58032133, compound

HRID 1429238Notes

Reaction equation

HRID 1429238 reaction equation
FC(F)(F)S(O[C:7]1[CH2:8][CH2:9][N:10]([C:13]2[C:18]([F:19])=[CH:17][C:16]([N+:20]([O-:22])=[O:21])=[CH:15][C:14]=2[F:23])[CH2:11][CH:12]=1)(=O)=O.[F:26][C:27]1[CH:28]=[C:29](B2OC(C)(C)C(C)(C)O2)[CH:30]=[CH:31][C:32]=1[F:33].[Cl-].[Li+].C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:19][C:18]1[CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=[C:14]([F:23])[C:13]=1[N:10]1[CH2:11][CH:12]=[C:7]([C:30]2[CH:29]=[CH:28][C:27]([F:26])=[C:32]([F:33])[CH:31]=2)[CH2:8][CH2:9]1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 534290432-(3,4-Difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 58031995Methanesulfonic acid, 1,1,1-trifluoro-, 1-(2,6-difluoro-4-nitrophenyl)-1,2,3,6-tetrahydro-4-pyridinyl ester

Product 1

HCID 58032133HCID 58032133, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1-(2,6-difluoro-4-nitrophenyl)-1,2,3,6-tetrahydropyridin-4-yl trifluoromethanesulfonate (1.18 g, 3.04 mmol), 2-(3,4-difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.02 g, 4.25 mmol), lithium chloride (0.387 g, 9.12 mmol) and a 2.0 M aq. solution of sodium carbonate (4.56 mL, 9.12 mmol) in anhydrous DME (15 mL) was vigorously stirred while bubbling with N2 gas for 20 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.176 g, 0.152 mmol) was added, and the resulting mixture was degassed for 5 minutes more. The reaction flask was equipped with a condenser and placed in 100° C. oil bath. The dark mixture was stirred at 100° C. under a dry N2 atmosphere for 16 hours, and was then cooled to room temperature and partitioned between water (50 mL) and EtOAc (2×50 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo, and the crude product was purified by column chromatography on silica gel using a solvent gradient of 0-40% EtOAc in hexanes to provide a yellow oil that solidified on standing. The solid was triturated with Et2O and hexanes, filtered and dried to provide the title compound (0.67 g, 63%).

Workup

  1. customwhile bubbling with N2 gas for 20 minutes
  2. customthe resulting mixture was degassed for 5 minutes more
  3. customThe reaction flask was equipped with a condenser
  4. customplaced in 100° C.
  5. temperaturewas then cooled to room temperature
  6. custompartitioned between water (50 mL) and EtOAc (2×50 mL)
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customthe crude product was purified by column chromatography on silica gel using a solvent gradient of 0-40% EtOAc in hexanes
  11. customto provide a yellow oil that
  12. customThe solid was triturated with Et2O and hexanes
  13. filtrationfiltered
  14. customdried

Sources & evidence

ORD record
ord-3bcfcedad0834dec8dd9037c5bfee6a8
Source dataset
uspto-grants-2015_01
Patent number
US08937150B2

Reaction notes

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