Nitrogen-based adducts derived from methyltrioxorhenium(VII) and mono- and polihalogenated pyridines are excellent stable catalysts for the selective epoxidation of 1-hexene. On the other hand, moderate stereoinduction values can be achieved when determined prochiral olefins are epoxidized with chiral rhenium(VII) complexes formed with the amines (S)-2-aminomethylpyrrolidine, (R)-(+)-phenyl ethylamine, and L-prolinamide as catalysts.