3-Cyanopyridine → (S)-3-oxiranylpyrrolidine-1-carboxylic acid t-butyl ester

HRID 1261802Notes

Reaction equation

HRID 1261802 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][C@H:10]([CH:13]=[CH2:14])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].N1C=CC=C(C#N)C=1.[OH:23]O>C[Re](=O)(=O)=O>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][C@H:10]([CH:13]2[CH2:14][O:23]2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 793-CyanopyridineHCID 784Hydrogen PeroxideHCID 46222798(R)-tert-Butyl 3-vinylpyrrolidine-1-carboxylate

Product 1

HCID 86650332(S)-3-oxiranylpyrrolidine-1-carboxylic acid t-butyl ester

Reagents, catalysts & solvents 1

HCID 178477782HCID 178477782, compoundCatalyst2×

Procedure

To (R)-3-vinylpyrrolidine-1-carboxylic acid t-butyl ester (6.1 g, 30.8 mmol, 1.0 eq.) was added 3-pyridinecarbonitrile (320 mg, 3.1 mmol, 0.1 eq.) and methyltrioxorhenium (VII) (192 mg, 769 mmol, 0.025 eq.). The mixture was stirred until homogeneous. 30% Hydrogen peroxide (33:77, hydrogen peroxide:H2O, 4.1 mL, 1.3 eq.) was added, and the mixture was placed in a ice water bath and stirred for 2 hours. Additional methyltrioxorhenium (VII) (50 mg) was added. The organic layer was collected and washed with a saturated sodium metabisulfite solution under an ice bath. The material was then washed with saturated aqueous NaCl. The organic layer was collected, dried over Na2SO4, filtered, and concentrated. The peroxide layer was carefully quenched by adding ice followed by adding saturated sodium metabisulfite solution dropwise at 0° C. The crude product was purified by column chromatography (0-100% EtOAc in hexanes) to give (S)-3-oxiranylpyrrolidine-1-carboxylic acid t-butyl ester as a yellowish oil (4.2 g).

Workup

  1. customthe mixture was placed in a ice water bath
  2. stirringstirred for 2 hours
  3. customThe organic layer was collected
  4. washwashed with a saturated sodium metabisulfite solution under an ice bath
  5. washThe material was then washed with saturated aqueous NaCl
  6. customThe organic layer was collected
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe peroxide layer was carefully quenched
  11. additionby adding ice
  12. additionby adding saturated sodium metabisulfite solution dropwise at 0° C
  13. customThe crude product was purified by column chromatography (0-100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-bda97f6c92104acc9193786aaa8d7be3
Source dataset
uspto-grants-2013_06
Patent number
US08471040B2

Reaction notes

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