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Synthesis of (E)-alpha-hydroxy-beta,gamma-unsaturated amides with high selectivity from alpha,beta-epoxyamides by
José M Concellón1, Pablo L Bernad, Eva Bardales
1Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, E-33071 Oviedo, Spain. jmcg@sauron.quimica.uniovi.es
Abstract:
The highly stereoselective synthesis of (E)-alpha-hydroxy-beta,gamma-unsaturated amides starting from alpha,beta-epoxyamides, by using catalytic SmI2 or SmI3, was achieved. This transformation can also be carried out by using SmI2 generated in situ from samarium powder and diiodomethane. The starting compounds 1 are easily prepared by the reaction of enolates derived from alpha-chloroamides with ketones at -78 degrees C. A mechanism to explain this transformation has been proposed. Cyclopropanation of (E)-alpha-hydroxy-beta,gamma-unsaturated amides has been performed to demonstrate their synthetic applications.
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