Trifluoromethanesulfonic anhydride → 2-Methyl-2,3-bis-trifluoromethanesulfonyloxy-propionic acid methyl ester

HRID 729602Notes

Reaction equation

HRID 729602 reaction equation
[O:1]([S:9]([C:12]([F:15])([F:14])[F:13])(=[O:11])=[O:10])S(C(F)(F)F)(=O)=O.[CH3:16][O:17][C:18](=[O:25])[C:19](CO)([CH3:22])[CH2:20][OH:21]>ClCCl.N1C(C)=CC=CC=1C>[CH3:16][O:17][C:18](=[O:25])[C:19]([CH3:22])([O:1][S:9]([C:12]([F:13])([F:14])[F:15])(=[O:10])=[O:11])[CH2:20][O:21][S:9]([C:12]([F:15])([F:14])[F:13])(=[O:10])=[O:1]

Participants

5

Reactant 2

HCID 67749Trifluoromethanesulfonic anhydrideHCID 87346Propanoic acid, 3-hydroxy-2-(hydroxymethyl)-2-methyl-, methyl ester

Product 1

HCID 874884802-Methyl-2,3-bis-trifluoromethanesulfonyloxy-propionic acid methyl ester

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 79372,6-LutidineSolvent

Procedure

Add Tf2O (80 mL) dropwise to a cool solution (−78° C.) of 3-hydroxy-2-hydroxymethyl-2-methyl-propionic acid methyl ester (Preparation 5, 32.5 g) in dichloromethane (400 mL) and 2,6-lutidine (80 mL). Allow the reaction to reach room temperature. and stir for about 2 hours. Dilute with dichloromethane (400 mL) and wash with HCl (3% aqueous solution). Dry the organic layer over MgSO4, filter and concentrate. Subject residue to silica gel chromatography eluting with hexanes/ethyl acetate 5%, to give 2-methyl-2,3-bis-trifluoromethanesulfonyloxy-propionic acid methyl ester as a colorless oil. 1H NMR (CDCl3, 300 MHz): δ ppm 4.7 (d, 2H, J=10.3 Hz), 4.5 (d, 2H, J=10.3 Hz), 3.8 (s, 3H), 1.4 (s, 3H).

Workup

  1. customthe reaction
  2. customto reach room temperature
  3. washwash with HCl (3% aqueous solution)
  4. dry with materialDry the organic layer over MgSO4
  5. filtrationfilter
  6. concentrationconcentrate
  7. washSubject residue to silica gel chromatography eluting with hexanes/ethyl acetate 5%

Sources & evidence

ORD record
ord-c549a9020eb943c0a4e9011bd5d01b02
Source dataset
uspto-grants-2009_09
Patent number
US07582638B2

Reaction notes

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