title: Hetero-Diels-Alder reaction of phosphinyl and phosphonyl nitroso alkenes with conjugated dienes: an aza-Cope rearrangement.
abstract: Phosphorylated nitroso alkenes react with cyclic dienes such as cyclopentadiene or cyclohexadiene to afford hetero Diels-Alder-type cycloadducts where the nitroso alkene participates as dienophile component and the cyclic olefin acts as the 4π-electron (diene) system. Subsequent aza-Cope rearrangement affords highly functionalized 5,6-dihydro-4H-1,2-oxazines. Conversely, the reaction of TMS-substituted cyclopentadiene (dienophile) with nitroso alkenes as heterodienes leads directly to bicyclic 1,2-oxazines. Theoretical studies are in agreement with the experimental results and with the new aza-Cope rearrangement proposed.
authors: Departamento de Química Orgánica I, Facultad de Farmacia, Centro de Investigaciones y Estudios Avanzados Lucio Lascaray, Universidad del País Vasco, Apartado 450, 01080 Vitoria, Spain.
authors: Jesús M
authors: JM
authors: de los Santos
authors: Roberto
authors: R
authors: Ignacio
authors: Gloria
authors: G
authors: Rubiales
authors: Domitila
authors: D
authors: Aparicio
authors: Francisco
authors: F
authors: Palacios
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D009603:Nitroso Compounds; D009943:Organophosphorus Compounds; D010720:Phosphines