Triethyl phosphite → (1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester

HRID 492256Notes

Reaction equation

HRID 492256 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[C@@H:9](OS(C)(=O)=O)[C@H:8]([N:22]=[N+]=[N-])[CH:7]=1)=[O:5])[CH3:2].[P:25]([O:32]CC)([O:29][CH2:30][CH3:31])[O:26][CH2:27][CH3:28]>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[C@@H:9]2[C@@H:8]([N:22]2[P:25]([O:29][CH2:30][CH3:31])([O:26][CH2:27][CH3:28])=[O:32])[CH:7]=1)=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 31215Triethyl phosphite2×HCID 86628951(3R,4S,5R)-3-Azido-4,5-bis-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester

Product 1

HCID 44221277(1S,5R,6S)-7-(diethoxy-phosphoryl)-5-methanesulfonyloxy-7-aza-bicyclo[4.1.0]hept-2-ene-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 383.4 mg of 14 and 4.0 mL toluene in a 10 mL round-bottom flask equipped with a magnetic stirrer, a reflux condenser maintained under an argon atmosphere at RT was added, 191 μl of triethyl phosphite. Nitrogen evolution began in about 5 min and after 30 min at RT the light yellow reaction mixture was heated to reflux for 5 h, then an additional 191 μl of triethyl phosphite were added and refluxing continued for another 2 h. The reaction mixture was cooled and evaporated at 40° C./60-10 mbar to yield 470 mg of the crude product as a yellow oil. The crude product was purified by SiO2 column chromatography using a 2/1 mixture of toluene and acetone. The combined fractions were evaporated and dried on a rotary evaporator 40° C./250-10 mbar to afford 87 mg of 16 as a yellow oil.

Workup

  1. additionwas added
  2. temperaturethe light yellow reaction mixture was heated
  3. temperatureto reflux for 5 h
  4. temperaturerefluxing
  5. waitcontinued for another 2 h
  6. temperatureThe reaction mixture was cooled
  7. customevaporated at 40° C./60-10 mbar
  8. customto yield 470 mg of the crude product as a yellow oil
  9. customThe crude product was purified by SiO2 column chromatography
  10. additiona 2/1 mixture of toluene and acetone
  11. customThe combined fractions were evaporated
  12. customdried on a rotary evaporator 40° C./250-10 mbar

Sources & evidence

ORD record
ord-8dd51e2a1f5b4b5db9f1fd990df3f1ba
Source dataset
uspto-grants-2009_05
Patent number
US07531687B2

Reaction notes

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