Tributylstannane → (6R,7S)-2,2-dimethyl-7-(1-hydroxy-1-methylethyl)-1-aza-3-oxabicyclo[4,2,0]-octan-8-one

HRID 1719320Notes

Reaction equation

HRID 1719320 reaction equation
[CH3:1][C:2]1([CH3:17])[O:9][CH2:8][CH2:7][C@H:6]2[N:3]1[C:4](=[O:16])[C@@:5]2([C:12]([OH:15])([CH3:14])[CH3:13])[N+]#[C-].C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N>C1C=CC=CC=1>[CH3:1][C:2]1([CH3:17])[O:9][CH2:8][CH2:7][C@H:6]2[N:3]1[C:4](=[O:16])[C@@H:5]2[C:12]([OH:15])([CH3:13])[CH3:14]

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 53810652(6R,7R)-2,2-dimethyl-7-(1-hydroxy-1-methylethyl)-7-isocyano-1-aza-3-oxabicyclo[4.2.0]octan-8-one

Product 1

HCID 13194415(6R,7S)-2,2-dimethyl-7-(1-hydroxy-1-methylethyl)-1-aza-3-oxabicyclo[4,2,0]-octan-8-one

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a mixture of (6R,7R)-2,2-dimethyl-7-(1-hydroxy-1-methylethyl)-7-isocyano-1-aza-3-oxabicyclo[4.2.0]octan-8-one and its (6R,7S)-isomer (2.5 g) in benzene (75 ml) were added tributyltinhydride (3.07 ml) and azobisisobutyronitrile (170 mg) at ambient temperature and the mixture was refluxed for 30 minutes. The reaction mixture was chromatographed on silica gel (65 g) eluting with a mixture of methylene chloride and acetone (10:1-2:1) to give a crude product, which was purified by silica gel (75 g) chromatography (hexane and ethyl acetate) to give (6R,7S)-2,2-dimethyl-7-(1-hydroxy-1-methylethyl)-1-aza-3-oxabicyclo[4,2,0]-octan-8-one (0.545 g) [(6R,7S)-isomer] and its (6R,7R)-isomer (1.406 g).

Workup

  1. temperaturethe mixture was refluxed for 30 minutes
  2. customThe reaction mixture was chromatographed on silica gel (65 g)
  3. washeluting with a mixture of methylene chloride and acetone (10:1-2:1)
  4. customto give a crude product, which
  5. customwas purified by silica gel (75 g) chromatography (hexane and ethyl acetate)

Sources & evidence

ORD record
ord-21de079e9d584367b726294fb44f23fa
Source dataset
uspto-grants-1985_09
Patent number
US04539152

Reaction notes

Loading…