Pyridine → (1R,2R,3R,5R,6R)-2-azido-6-fluoro-3-trifluoromethanesulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester

HRID 130499Notes

Reaction equation

HRID 130499 reaction equation
N1C=CC=CC=1.FC(F)(F)S([O:12][S:13]([C:16]([F:19])([F:18])[F:17])(=[O:15])=[O:14])(=O)=O.[CH2:22]([O:24][C:25]([C@:27]1([N:40]=[N+:41]=[N-:42])[C@H:32](O)[CH2:31][C@@H:30]2[C@H:28]1[C@@:29]2([F:39])[C:34]([O:36][CH2:37][CH3:38])=[O:35])=[O:26])[CH3:23].CCOCC>ClCCl>[CH2:22]([O:24][C:25]([C@:27]1([N:40]=[N+:41]=[N-:42])[C@H:32]([O:12][S:13]([C:16]([F:17])([F:18])[F:19])(=[O:14])=[O:15])[CH2:31][C@@H:30]2[C@H:28]1[C@@:29]2([F:39])[C:34]([O:36][CH2:37][CH3:38])=[O:35])=[O:26])[CH3:23]

Participants

6

Reactant 4

HCID 1049Pyridine2×HCID 3283Diethyl EtherHCID 67749Trifluoromethanesulfonic anhydride2×HCID 11162402(1R,2R,3R,5R,6R)-2-azido-6-fluoro-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester

Product 1

HCID 11154739(1R,2R,3R,5R,6R)-2-azido-6-fluoro-3-trifluoromethanesulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

48 μL of pyridine and 78 μL of trifluoromethane sulfonic acid anhydride dissolved in 0.4 mL of dichloromethane were added dropwise to 120 mg of (1R,2R,3R,5R,6R)-2-azido-6-fluoro-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester dissolved in 20 mL of dichloromethane at −75° C., and the mixture was stirred for 1.5 hours at ice-cooling under a nitrogen atmosphere. 24 μL of pyridine and 39 μL of trifluoromethane sulfonic acid anhydride dissolved in 0.2 mL of dichloromethane were added dropwise thereto at −75° C., and the mixture was stirred for 25 minutes at ice-cooling. 10 mL of ether was added thereto, and after the solids were filtered off, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel: Wako gel C200, eluent: hexane-ethyl acetate=5:1), thereby yielding 166 mg of (1R,2R,3R,5R,6R)-2-azido-6-fluoro-3-trifluoromethanesulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester.

Workup

  1. temperaturecooling under a nitrogen atmosphere
  2. additionwere added dropwise
  3. stirringat −75° C., and the mixture was stirred for 25 minutes at ice-
  4. temperaturecooling
  5. filtrationafter the solids were filtered off
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customthe residue was purified by column chromatography (silica gel: Wako gel C200, eluent: hexane-ethyl acetate=5:1)

Sources & evidence

ORD record
ord-f870bbdbea3f49b08af61cd495e4b3df
Source dataset
uspto-grants-2008_06
Patent number
US07381746B2

Reaction notes

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