Formic Acid → HCID 56623594, compound

HRID 1719266Notes

Reaction equation

HRID 1719266 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH:20]([OH:22])=[O:21].O[CH:24]([C@@H:26]1[C@@H:29]([S:30][CH3:31])[N:28]([C:32](=[C:37]([CH3:39])[CH3:38])[C:33]([O:35][CH3:36])=[O:34])[C:27]1=[O:40])[CH3:25].N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH:20]([O:22][CH:24]([C@@H:26]1[C@@H:29]([S:30][CH3:31])[N:28]([C:32](=[C:37]([CH3:39])[CH3:38])[C:33]([O:35][CH3:36])=[O:34])[C:27]1=[O:40])[CH3:25])=[O:21]

Participants

6

Reactant 4

HCID 284Formic AcidHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 56636482HCID 56636482, compound

Product 1

HCID 56623594HCID 56623594, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of triphenylphosphine (1.647 g), formic acid (0.20 ml), and a mixture (1:3) of methyl 2-[(3S,4R)-3-{(1RS)-1-hydroxyethyl}-4-methylthio-2-oxoazetidin-1-yl]-3-methylbut-2-enoate (1.145 g) in tetrahydrofuran (14 ml) was added dropwise diethyl azodicarboxylate (0.83 ml) at 0° C. under a nitrogen atmosphere. After keeping at the same temperature for 15 minutes, the solution was allowed to warm to room temperature and stirred for two hours. The mixture was cooled to 0° C. and additional fornic acid (24 μl) and diethyl azodicarboxylate (0.10 ml) were added. After stirring at room temperature for one hour, the solution was concentrated, taken up into ethyl acetate (60 ml) and washed with a chilled dilute aqueous sodium bicarbonate, water, and brine. The organic layer was dried over magnesium sulfate, evaporated and re-dissolved in benzene (20 ml) to result in precipitation of crystals. These crystals were collected and washed with benzene. The combined filtrate and washings were evaporated and chromatographed on silica gel (60 g) eluting with 10-30% ethyl acetate in hexane to give a mixture (5:1) of methyl 2-[(3S,4R)-3-{(1RS)-1-formyloxyethyl}-4-methylthio-2-oxoazetidin-1-yl]-3-methylbut-2-enoate (889 mg).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. stirringAfter stirring at room temperature for one hour
  3. concentrationthe solution was concentrated
  4. washwashed with a chilled dilute aqueous sodium bicarbonate, water, and brine
  5. dry with materialThe organic layer was dried over magnesium sulfate
  6. customevaporated
  7. dissolutionre-dissolved in benzene (20 ml)
  8. customto result in precipitation of crystals
  9. customThese crystals were collected
  10. washwashed with benzene
  11. customThe combined filtrate and washings were evaporated
  12. customchromatographed on silica gel (60 g)
  13. washeluting with 10-30% ethyl acetate in hexane

Sources & evidence

ORD record
ord-2e4a345c7df9429790379014efc3261d
Source dataset
uspto-grants-1985_09
Patent number
US04539152

Reaction notes

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