Markovnikov versus anti-Markovnikov selectivity in the amination of terminal olefins coordinated to platinum(II)

The products of addition of secondary amines to platinum(II)-coordinated terminal olefins undergo a fast Markovnikov (M)–anti-Markovnikov (anti-M) isomerization process leading, to an equilibrium composition different from that obtained under kinetic control; in basic medium, the amination products undergo intramolecular ring closing reaction which is faster for the anti-M isomers, so decreasing the M/anti-M ratio in the final complexes.