Ruthenium-oxo and -tosylimido porphyrin complexes for epoxidation and aziridination of alkenes

Dioxoruthenium(VI) porphyrins including those containing chiral porphyrinato ligands can be readily prepared by oxidation of [Ru11(Por)(CO)(MeOH)] with PhIO or metachloroperoxybenzoic acid. Similar reactions with PhINTs gave [RuVI(Por)(NTs)2] isolated as air stable solids at room temperature. The [RuVI(Por)O2] complexes are competent oxidants for epoxidation of alkenes with high selectivities. Enantioselective epoxidation of alkenes giving the corresponding organic epoxides with moderate to good enantioselectivites have also been achieved using chiral [RuVI(D4-Por)O2] [D4-H2Por= 5,10,15,20-tetrakis-(IS,4R,5R,8S-1,2,3,4,5,6,7,8-octahydro-1,4:5,8- dimethanoanthracen-9-yl)porphyrin] and [RuVI(D2-Por)O2] complexes. The mechanism of alkene epoxidation by [RuVI(Por)O2] has been examined. Procedures for catalytic epoxidation of alkenes using ruthenium porphyrin catalysts has also been developed. [RuVI(Por)(NTs)2] was found to undergo aziridination of alkenes and amidation of alkanes in organic solvents at room temperature.