(Triphenylphosphoranylidene)acetaldehyde → methylene-(2S,5R)-6-[(E)-formylmethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

HRID 1981207Notes

Reaction equation

HRID 1981207 reaction equation
[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[CH:15]2[N:12]([C:13](=[O:17])[C:14]2=O)[CH:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].[CH:23]([CH:25]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:24]>C1C=CC=CC=1>[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:25]\[CH:23]=[O:24])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:2]/[CH:1]=[O:6])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21]

Participants

5

Reactant 2

HCID 75051(Triphenylphosphoranylidene)acetaldehydeHCID 86740043Methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Product 2

HCID 86740052methylene-(2S,5R)-6-[(E)-formylmethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalateHCID 86740054methylene-(2S,5R)-6-[(Z)-formylmethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 3.8 g of methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate in 100 ml of benzene is treated at 20° with 3.5 g of formylmethylenetriphenylphosphorane. After 10 minutes, the reaction mixture is evaporated. The residue is chromatographed on silica gel while eluting with n-hexane/ethyl acetate (8:2). There are obtained methylene-(2S,5R)-6-[(E)-formylmethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate [Rf: 0.27; cyclohexane/ethyl acetate (8:2); NMR (CDCl3), δ (ppm): 5.68 (1H3); 5.9 (1H5); 6.24 (1H); 10.3 (1H)] and methylene-(2S,5R)-6-[(Z)-formylmethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate [Rf: 0.2; cyclohexane/ethyl acetate (8:2); NMR (CDCl3), δ (ppm): 5.68 (1H3); 6.12 (1H 5); 6.55 (1H); 9.86 (1H)].

Workup

  1. customthe reaction mixture is evaporated
  2. customThe residue is chromatographed on silica gel
  3. washwhile eluting with n-hexane/ethyl acetate (8:2)

Sources & evidence

ORD record
ord-f62b4ac7112a471d92d71159f1f59e87
Source dataset
uspto-grants-1985_04
Patent number
US04512999

Reaction notes

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