Triacetoxyperiodinane → HCID 86674957, compound

HRID 1502382Notes

Reaction equation

HRID 1502382 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:7]([C:10]#[C:11][C:12]2[CH:17]=[C:16]([F:18])[CH:15]=[CH:14][C:13]=2[CH3:19])=[CH:8][N:9]=1)[CH:5]=[O:6].[CH3:20][Mg]Cl.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>O1CCCC1.ClCCl>[Cl:1][C:2]1[CH:3]=[C:4]([C:5](=[O:6])[CH3:20])[C:7]([C:10]#[C:11][C:12]2[CH:17]=[C:16]([F:18])[CH:15]=[CH:14][C:13]=2[CH3:19])=[CH:8][N:9]=1

Participants

6

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 86674958HCID 86674958, compoundHCID 178418332HCID 178418332, compound

Product 1

HCID 86674957HCID 86674957, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 2-chloro-5-((5-fluoro-2-methylphenyl)ethynyl)isonicotinaldehyde (705 mg, 2.6 mmol) in tetrahydrofuran (11 mL) cooled at −15° C. was added a solution of 3.0M methylmagnesium chloride in tetrahydrofuran (1 mL, 3.1 mmol) dropwise over 1 minute. The reaction mixture was stirred at this temperature for 15 minutes and then quenched with a few drops of saturated aqueous ammonium chloride solution, tetrahydrofuran was evaporated in vacuo, and the resulting residue was redissolved in dichloromethane (50 mL) and washed with water (50 mL). The organic layer was separated, dried over sodium sulfate, filtered, and evaporated in vacuo to afford a colorless oil that was redissolved in dichloromethane (10 mL) and treated with Dess-Martin periodinane (1.4 g, 3.4 mmol). The reaction mixture was stirred at room temperature for 1 hour, and then diluted with dichloromethane (100 mL) and washed with saturated aqueous sodium bicarbonate solution (50 mL). The organic layer was separated, dried over sodium sulfate, filtered, and evaporated in vacuo to afford a residue that was purified by flash chromatography (silica, 40 g, ISCO, 0-50% ethyl acetate in heptane) to afford the title compound as a pale yellow solid (700 mg, 90%), which was used in the next step without further purification.

Workup

  1. customquenched with a few drops of saturated aqueous ammonium chloride solution, tetrahydrofuran
  2. customwas evaporated in vacuo
  3. dissolutionthe resulting residue was redissolved in dichloromethane (50 mL)
  4. washwashed with water (50 mL)
  5. customThe organic layer was separated
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto afford a colorless oil that
  10. stirringThe reaction mixture was stirred at room temperature for 1 hour
  11. washwashed with saturated aqueous sodium bicarbonate solution (50 mL)
  12. customThe organic layer was separated
  13. dry with materialdried over sodium sulfate
  14. filtrationfiltered
  15. customevaporated in vacuo
  16. customto afford a residue that
  17. customwas purified by flash chromatography (silica, 40 g, ISCO, 0-50% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-dae192ec71154e4e996718a39d5210e2
Source dataset
uspto-grants-2015_12
Patent number
US09206175B2

Reaction notes

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