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α’-Oxy Enones for Construction of All-Carbon Quaternary Stereogenic Centers: Azlactones as Pronucleophiles
1 , 1 , 1 , 1 , 1 , 1 , 2 , 2 , 2 , 1 , * 1
1  Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco, Manuel Lardizabal 3, 20018 Donostia, Spain
2  Departamento de Química Aplicada, Universidad Pública de Navarra, Campus de Arrosadía, 31006 Pamplona, Spain


Studies in our group have shown that α’-oxy enones react in the presence of Brønsted base catalysts with 3-substituted oxindoles, cyanoesters, 5H-oxazol-4-ones, 1H-imidazol-4-(5H)-ones and azlactones to give the corresponding 1,5-dicarbonyl Michael adducts with a fully substituted carbon center in high enantioselectivity. For example, the reaction between azlactones 2 and enone 1 is efficiently promoted by catalyst C1 to led, after desilylation, to the corresponding products 3 with good yields and ee’s. In each case, reactions proceed with high site selectivity and no products from reaction at the C2-possition of the azlactone ring are observed. Besides their utility for the installation of aldehyde and ketone functionality, α’-oxy enones, through simple oxidative cleavage of the ketol moiety in the resulting adducts, act as α-β-unsaturated carboxylic acid surrogates for which successful methodologies are notably deficient.

Keywords: Brønsted base catalysts; Michael adducts; Enantioselectivity; α’-oxy enones