Trifluoroacetamide → HCID 131734805, compound

HRID 1778154Notes

Reaction equation

HRID 1778154 reaction equation
FC(F)(F)C([NH2:5])=O.[O-2].[Mg+2].[C:10]([Si:14]([CH3:23])([CH3:22])[O:15][CH2:16][CH2:17][CH2:18][S:19]([CH3:21])=[O:20])([CH3:13])([CH3:12])[CH3:11].C(OI(C1C=CC=CC=1)OC(=O)C)(=O)C>ClCCl.C([O-])(=O)C.[Rh+2].C([O-])(=O)C>[C:10]([Si:14]([CH3:22])([CH3:23])[O:15][CH2:16][CH2:17][CH2:18][S:19]([CH3:21])(=[NH:5])=[O:20])([CH3:13])([CH3:12])[CH3:11]

Participants

7

Reactant 4

HCID 67717TrifluoroacetamideHCID 76724Iodobenzene diacetateHCID 6850729Magnesium monoxideHCID 123824470HCID 123824470, compound

Product 1

HCID 131734805HCID 131734805, compoundYield 65.5%

Reagents, catalysts & solvents 2

HCID 21674Acetic acid, rhodium(2+) saltCatalystHCID 6344DichloromethaneSolvent

Procedure

To a 1-L round-bottom flask containing 2,2,2-trifluoroacetamide (17.43 g), magnesium oxide (12.1 g), and rhodium(II) acetate (0.99 g) in anhydrous dichloromethane (500 mL) was added tert-butyldimethyl(3-(methylsulfinyl)propoxy)silane (17.65 g) and (diacetoxyiodo)benzene (36.1 g). The resulting reaction mixture was stirred at room temperature for 24 hours and then filtered through a short pad of celite. The filtrate was concentrated, the brown oily residue was taken up in MeOH (˜500 mL), and potassium carbonate (51.7 g) was added. The reaction mixture was stirred at RT for 2 hours. The mixture was then filtered through a pad of celite, the pad was washed with MeOH, and the filtrate was concentrated. The resulting soft brown solid was treated with DCM-EtOAc (4:1), the mixture was stirred at room temperature for 1 hour, and it was filtered again through a pad composed of silica gel and celite. The pad was washed with DCM-EtOAc (2:1) first and then with neat EtOAc only. The filtrate was concentrated and the brown oily residue was subject to a column chromatography (EtOAc-Hex 1:2 to neat EtOAc). Concentration of the product eluting fractions gave the title compound as a light brown oil (12.3 g).

Workup

  1. customThe resulting reaction mixture
  2. filtrationfiltered through a short pad of celite
  3. concentrationThe filtrate was concentrated
  4. additionpotassium carbonate (51.7 g) was added
  5. stirringThe reaction mixture was stirred at RT for 2 hours
  6. filtrationThe mixture was then filtered through a pad of celite
  7. washthe pad was washed with MeOH
  8. concentrationthe filtrate was concentrated
  9. additionThe resulting soft brown solid was treated with DCM-EtOAc (4:1)
  10. stirringthe mixture was stirred at room temperature for 1 hour
  11. filtrationit was filtered again through a pad
  12. washThe pad was washed with DCM-EtOAc (2:1) first
  13. concentrationThe filtrate was concentrated
  14. washConcentration of the product eluting fractions

Sources & evidence

ORD record
ord-c19d6b86741e4264a40856f2feb1ae33
Source dataset
uspto-grants-2016_02
Patent number
US09266869B2

Reaction notes

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