New catalytic reactions of (unsaturated) nitriles via metal-ligand cooperative activation of the C≡N bond

Abstract

The nitrile functional group is a very versatile intermediate which can be converted into amides, carboxylic acids, amines and imines, and thus, catalytic conversion of the C≡N bond under mild condition is an important field from an organic synthetic perspective. Recent developments in the area of transition metal pincer complexes has created new possibilities in this area, generally via efficient pathways and under mild conditions. Especially, non-innocent ligands enable the corresponding transition metal complexes to active nitriles via metal-ligand cooperation (e.g. Milstein Ru PNN complex). This new approach allows chemists to explore new challenging reactions with nitriles under mild conditions. The research described in this thesis was aimed at the catalytic (conjugate) addition of weak nucleophiles to (unsaturated) nitriles using transition metal pincer complexes via a metal-ligand cooperative pathway. In addition, chiral transition metal pincer complexes were synthesized and further evaluated in the enantioselective conjugate addition of alcohols to α,β-unsaturated nitriles.