Enantioselective epoxidation reaction of non-functionalised prochiral alkenes using optically resolved [brucine](R)-[Ru(PDTA-H)Cl] and [brucine](S)-[Ru(PDTA-H)Cl] complexes

The racemic metal complex KRu(PDTA-H)Cl]¹ has been resolved into its optical isomers using brucine as the resolving agent counter ion, brucine](S)-Ru(PDTA-H)Cl] (1) and brucine](R)-Ru(PDTA-H)Cl] (2) and their structures are determined by single crystal X-ray methods. Longer Ru–Cl bonds in both the complexes (2.3974(13)A in 1 and 2.415(6) in 2 along with one relatively weaker and strained chelation ring could be responsible for their catalytic activity. The CD pattern of the complex 1 shows the presence of the two isomers λ and δ with more contribution of λ form while the complex 2 acquire only λ conformation. Catalytic activity of 1 and 2 for enantioselective epoxidation of non-functionalised alkenes viz. styrene, 4-chloro-, 4-methyl-, 4-nitrostyrene, 1,2-dihydronaphthalene and indene was accomplished by using molecular oxygen and iodosyl benzene as terminal oxidant. Excellent conversions (85–89%) were obtained in case of 1,2-dihydronaphthalene with both the catalysts while catalyst 2 gave good conversion with styrene and 4-methylstyrene. The enantiomeric excess of the epoxide was determined by ¹H NMR using chiral shift reagent Eu(hfc)₃/ by chiral capillary column. The extent of enantioselectivity with respect to the substituents on substrate is shown on Hammet plot. A possible mechanism at the oxo transfer stage is also envisaged.