Unprecedent selectivity in the H2O2 epoxidation of simple alkenes imparted by soft Pt(II) Lewis acid catalysts

PETR 11

Giorgio Strukul, strukul@unive.it and Alessandro Scarso. Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy
The epoxidation of simple unfunctionalyzed terminal alkenes such as propene, 1-hexene, 1-octene, etc. has always been very challenging because of their intrinsically poor reactivity. Devising new catalysts capable of activating the substrate instead of the oxidant is crucial. We report the preparation of new soft Pt(II) Lewis acid catalysts that show exceptional activity in such reaction using H2O2 as the oxidant. Unprecedented selectivity is observed in the epoxidation of dienes (terminal and internal double bonds). Enantioselectivities up to 87% are observed using chiral-diphosphine modified catalysts. mechnistic insight shows that the reaction proceeds via direct activation of the olefin by the metal, followed by nucleophilic attack of the oxidant.