Sodium Azide → (3R,4R,5S)-5-azido-4-(diethoxy-phosphorylamino)-3-(1-ethyl-propoxy)-cyclohex-1-enecarboxylic acid ethyl ester

HRID 492261Notes

Reaction equation

HRID 492261 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@@H:10](OS(C)(=O)=O)[C@@H:9]([NH:17][P:18]([O:23][CH2:24][CH3:25])([O:20][CH2:21][CH3:22])=[O:19])[C@H:8]([O:26][CH:27]([CH2:30][CH3:31])[CH2:28][CH3:29])[CH:7]=1)=[O:5])[CH3:2].[N-:32]=[N+:33]=[N-:34].[Na+]>CCO.CS(C)=O.CCOC(C)=O.CC1CCCCC1>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@H:10]([N:32]=[N+:33]=[N-:34])[C@@H:9]([NH:17][P:18]([O:23][CH2:24][CH3:25])([O:20][CH2:21][CH3:22])=[O:19])[C@H:8]([O:26][CH:27]([CH2:30][CH3:31])[CH2:28][CH3:29])[CH:7]=1)=[O:5])[CH3:2]

Participants

7

Reactant 2

HCID 33557Sodium AzideHCID 44221278(3R,4S,5R)-4-(diethoxy-phosphorylamino)-3-(1-ethyl-propoxy)-5-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester

Product 1

HCID 57621536(3R,4R,5S)-5-azido-4-(diethoxy-phosphorylamino)-3-(1-ethyl-propoxy)-cyclohex-1-enecarboxylic acid ethyl esterYield 15.1%

Reagents, catalysts & solvents 4

HCID 679Dimethyl SulfoxideSolventHCID 702EthanolSolventHCID 7962MethylcyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
87.5 °C

Procedure

To a solution of 104 mg of 18 in 0.50 mL of EtOH and 0.50 mL of DMSO in a 5.0 mL round-bottom flask equipped with a magnetic stirrer, a reflux condenser and an inert gas supply was added 28 mg sodium azide and the reaction mixture was stirred at 85-90° C. for 20 h. The brown reaction mixture was cooled to RT diluted with 1.0 mL of EtOAc and extracted with 1.0 mL of aqueous 1 M NaHCO3. The separated organic phase was dried (Na2SO4), filtered and evaporated at 40° C./120-10 mbar to obtain 40 mg of the crude product as brown crystals. The crude product was dissolved in 0.40 mL methylcyclohexane, stirred for 5 h at RT. The white crystals which formed were filtered and washed with 0.15 mL of methylcyclohexane, dried at 40° C./10 mbar for 2 h to afford 14 mg of 26 as white crystals.

Workup

  1. temperatureThe brown reaction mixture was cooled to RT
  2. extractionextracted with 1.0 mL of aqueous 1 M NaHCO3
  3. dry with materialThe separated organic phase was dried (Na2SO4)
  4. filtrationfiltered
  5. customevaporated at 40° C./120-10 mbar
  6. customto obtain 40 mg of the crude product as brown crystals
  7. stirringstirred for 5 h at RT
  8. customThe white crystals which formed
  9. filtrationwere filtered
  10. washwashed with 0.15 mL of methylcyclohexane
  11. customdried at 40° C./10 mbar for 2 h

Sources & evidence

ORD record
ord-079bfe861d204b5085a081e8d8f406a6
Source dataset
uspto-grants-2009_05
Patent number
US07531687B2

Reaction notes

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