Acetic Anhydride → Ethyl (3R,4R,5S)-4-acetamido-5-azido-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylate

HRID 492263Notes

Reaction equation

HRID 492263 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@H:10]([N:12]=[N+:13]=[N-:14])[C@@H:9]([NH2:15])[C@H:8]([O:16][CH:17]([CH2:20][CH3:21])[CH2:18][CH3:19])[CH:7]=1)=[O:5])[CH3:2].[CH3:22][CH2:23][O:24]C(C)=O.C([O-])(O)=O.[Na+].C(OC(=O)C)(=O)C>CCCCCC.COC(C)(C)C>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@H:10]([N:12]=[N+:13]=[N-:14])[C@@H:9]([NH:15][C:23](=[O:24])[CH3:22])[C@H:8]([O:16][CH:17]([CH2:18][CH3:19])[CH2:20][CH3:21])[CH:7]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 7918Acetic AnhydrideHCID 8857Ethyl AcetateHCID 516892Sodium BicarbonateHCID 9882666(3R,4R,5S)-4-amino-5-azido-3-(1-ethyl-propoxy)-cyclohex-1-enecarboxylic acid ethyl ester

Product 1

HCID 9967681Ethyl (3R,4R,5S)-4-acetamido-5-azido-3-(1-ethylpropoxy)-1-cyclohexene-1-carboxylate

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

To a solution of 118.5 mg of 28 and 1.0 mL of EtOAc in a 5.0 mL round-bottom flask equipped with a magnetic stirrer and an inert gas supply was added 1.0 mL of aqueous 1 M NaHCO3. To the stirred mixture was added 45.4 μL of acetic anhydride and the mixture was stirred for 1 h at RT. The organic phase was separated and dried (Na2SO4, 1 g), filtered and the filter cake was washed with 2.0 mL EtOAc. The combined filtrates were evaporated at 40° C./240 to 10 mbar to afford 139 mg crude product as beige solid. The solid was suspended in 1.40 mL of n-hexane and 0.70 mL tert-butyl methyl ether, stirred for one h at RT, cooled to 0-5° C. and stirred for 2 h at 0-5° C. The suspension was filtered and the filter cake was washed with total 0.70 mL of a pre-cooled (0-5° C.) mixture of n-hexane and tert-butyl methyl ether (2/1). The filter cake was dried at 45° C./9 mbar to afford 94 mg of 30 as white crystals.

Workup

  1. customThe organic phase was separated
  2. dry with materialdried (Na2SO4, 1 g)
  3. filtrationfiltered
  4. washthe filter cake was washed with 2.0 mL EtOAc
  5. customThe combined filtrates were evaporated at 40° C./240 to 10 mbar
  6. customto afford 139 mg crude product as beige solid
  7. temperaturecooled to 0-5° C.
  8. stirringstirred for 2 h at 0-5° C
  9. filtrationThe suspension was filtered
  10. washthe filter cake was washed with total 0.70 mL of
  11. temperaturea pre-cooled
  12. addition(0-5° C.) mixture of n-hexane and tert-butyl methyl ether (2/1)
  13. customThe filter cake was dried at 45° C./9 mbar

Sources & evidence

ORD record
ord-fc879554a64549fda3e367ed227efc19
Source dataset
uspto-grants-2009_05
Patent number
US07531687B2

Reaction notes

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