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

HRID 130501Notes

Reaction equation

HRID 130501 reaction equation
FC(F)(F)S([O:6][S:7]([C:10]([F:13])([F:12])[F:11])(=[O:9])=[O:8])(=O)=O.[CH2:16]([O:18][C:19]([C@:21]1([N:34]=[N+:35]=[N-:36])[C@@H:26](O)[CH2:25][C@@H:24]2[C@H:22]1[C@@:23]2([F:33])[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[O:20])[CH3:17].N1C=CC=CC=1.C(OCC)C>ClCCl>[CH2:16]([O:18][C:19]([C@:21]1([N:34]=[N+:35]=[N-:36])[C@@H:26]([O:6][S:7]([C:10]([F:11])([F:12])[F:13])(=[O:8])=[O:9])[CH2:25][C@@H:24]2[C@H:22]1[C@@:23]2([F:33])[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[O:20])[CH3:17]

Participants

6

Reactant 4

HCID 1049PyridineHCID 3283Diethyl EtherHCID 67749Trifluoromethanesulfonic anhydrideHCID 11185694(1R,2R,3S,5R,6R)-2-azido-6-fluoro-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester

Product 1

HCID 86606013(1R,2R,3S,5R,6R)-2-azido-6-fluoro-3-trifluoromethanesulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-77 °C

Procedure

0.36 mL of trifluoromethane sulfonic acid anhydride dissolved in 1.2 mL of dichloromethane was added dropwise to 364 mg of (1R,2R,3S,5R,6R)-2-azido-6-fluoro-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester dissolved in 6.1 mL of dichloromethane and 0.21 mL of pyridine at −77° C. to −69° C., under a nitrogen atmosphere. The mixture was stirred for 30 minutes at −77° C., and further stirred for 30 minutes at ice-cooling. 30 mL of diethyl ether was added thereto, and after the solids were filtered off, the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel: Wako gel C200, eluent: hexane-ethyl acetate=5:1), thereby yielding 487 mg of (1R,2R,3S,5R,6R)-2-azido-6-fluoro-3-trifluoromethanesulfonyloxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid diethyl ester.

Workup

  1. customat −77° C. to −69° C.
  2. stirringfurther stirred for 30 minutes at ice-
  3. temperaturecooling
  4. filtrationafter the solids were filtered off
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customThe residue was purified by column chromatography (silica gel: Wako gel C200, eluent: hexane-ethyl acetate=5:1)

Sources & evidence

ORD record
ord-927355545dde4b4c8fd94e6ac22b8d76
Source dataset
uspto-grants-2008_06
Patent number
US07381746B2

Reaction notes

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