Ethyl Acetate → HCID 15086182, compound

HRID 1613996Notes

Reaction equation

HRID 1613996 reaction equation
[N+](=[C:3]([C:17](=O)[C@@H:18]([C@@H:20]1[C@@H:23]([C@H:24]([OH:26])[CH3:25])[C:22](=[O:27])[NH:21]1)[CH3:19])[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)=[O:5])=[N-].P(Cl)(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O.[N:46]1([CH2:51][C@@H:52]2[CH2:56][C@H:55]([SH:57])[CH2:54][N:53]2[C:58]([O:60][CH2:61][C:62]2[CH:67]=[CH:66][C:65]([N+:68]([O-:70])=[O:69])=[CH:64][CH:63]=2)=[O:59])[CH:50]=[CH:49][N:48]=[CH:47]1.C(OCC)(=O)C>ClCCCl.C(#N)C.C(N(C(C)C)CC)(C)C.C([O-])(=O)C.[Rh+2].C([O-])(=O)C>[OH:26][C@@H:24]([C@H:23]1[C:22](=[O:27])[N:21]2[C@@H:20]1[C@@H:18]([CH3:19])[C:17]([S:57][C@@H:55]1[CH2:54][N:53]([C:58]([O:60][CH2:61][C:62]3[CH:67]=[CH:66][C:65]([N+:68]([O-:70])=[O:69])=[CH:64][CH:63]=3)=[O:59])[C@H:52]([CH2:51][N:46]3[CH:50]=[CH:49][N:48]=[CH:47]3)[CH2:56]1)=[C:3]2[C:4]([O:6][CH2:7][C:8]1[CH:9]=[CH:10][C:11]([N+:14]([O-:16])=[O:15])=[CH:12][CH:13]=1)=[O:5])[CH3:25]

Participants

9

Reactant 4

HCID 8857Ethyl AcetateHCID 75654Diphenyl chlorophosphateHCID 15086181HCID 15086181, compoundHCID 57009450(R)-4-Nitrobenzyl 2-diazo-4-((2R,3S)-3-((R)-1-hydroxyethyl)-4-oxoazetidin-2-yl)-3-oxopentanoate

Product 1

HCID 15086182HCID 15086182, compoundYield 37.5%

Reagents, catalysts & solvents 4

HCID 21674Acetic acid, rhodium(2+) saltCatalystHCID 111,2-DichloroethaneSolventHCID 6342AcetonitrileSolvent2×HCID 81531DiisopropylethylamineSolvent

Conditions

Temperature
-7.5 °C

Procedure

To a solution of 4-nitrobenzyl (4R)-2-diazo-4-[(2R,3S)-3-{(1R)-1-hydroxyethyl}-4-oxoazetidin-2-yl]-3-oxopentanoate (0.28 g) in 1.2-dichloroethane (15 ml) was added rhodium (II) acetate (2 mg) under reflux. The mixture was reluxed for 30 minutes under nitrogen atmosphere and concentrated under reduced pressure to give a syrup. The syrup was dissolved in acetonitrile (15 ml) and N,N-diisopropyl-N-ethylamine (0.37 ml). Diphenyl chlorophosphate (0.16 ml) was added thereto at -10--5° C. in a nitrogen stream, followed by stirring at -10--5° C. for 30 minutes. To the solution were added a solution of (2S,4S)-2-(imidazol-1-yl)methyl-4-mercapto-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (0.26 g) in acetonitrile (2 ml) at -30--25° C. and the mixture was stirred at 0-10° C. for 2 hours. The mixture was poured into ethyl acetate (75 ml), washed with water (50 ml ×2), dried over magnesium sulfate and concentrated under reduced pressure to give a syrup. The syrup was subjected to a column chromatography on sili.COPYRGT.a gel (20 g) and eluted with a mixture of acetone and dichloromethane (50:50, V/V) to give 4-nitrobenzyl (4R,5S,6S)-6-[(lR)-1-hydroxyethyl]-3-[(2S,4S)-2-(imidazol-1-yl)methyl-1-(4-nitrobenzyloxycarbonyl)pyrrolidin-4-yl]thio-4-methyl -7-oxo-1-azabicyclo[3.2.0]-hept-2-ene-2-carboxylate (0.19 g).

Workup

  1. temperatureunder reflux
  2. concentrationconcentrated under reduced pressure
  3. customto give a syrup
  4. customat -10--5° C.
  5. stirringthe mixture was stirred at 0-10° C. for 2 hours
  6. washwashed with water (50 ml ×2)
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customto give a syrup
  10. washeluted with a mixture of acetone and dichloromethane (50:50, V/V)

Sources & evidence

ORD record
ord-44945ea31a5e4919bb0795fe8860ad37
Source dataset
uspto-grants-1993_03
Patent number
US05194624

Reaction notes

Loading…