Studies towards the catalytic anti-Markovnikov functionalisation of alkenes

Abstract

In 1986 Jensen and Trogler reported that a biphasic system containing the mononuclear complex trans-[(Me₃P)₂PtHCl] and NaOH catalysed the anti-Markovnikov hydration of 1-hexene to 1-hexanol. The unusual method of preparation could also give rise to dinuclear complexes with bridging hydride ligands. We have tested some dinuclear complexes for catalytic activity and discovered that on heating these yield trinuclear complexes. Using the independently prepared trinuclear complex [(dppe)₃Pt₃H₃]⁺, we found that it acted as a catalyst for the reaction between 1-octene and methanol to give 1-methoxyoctane, although the results were somewhat erratic. A cause of the erratic behaviour was found to be the presence of varying amounts of hydroperoxide impurities, which underwent a Hock rearrangement in acidic conditions.