Mechanism of the asymmetric hydrogenation of exocyclic α,β-unsaturated carbonyl compounds with an iridium/BiphPhox catalyst: NMR and DFT studies

Abstract

The mechanism of the asymmetric hydrogenation of exocyclic α,β-unsaturated carbonyl compounds with the (aS)-Ir/iPr-BiphPhox catalyst was studied by NMR experiments and DFT computational analyses. Computed optical yields of the asymmetric hydrogenation proceeding by an iridium(I)/iridium(III) mechanism involving a transition state stabilized through two intramolecular hydrogen bonds are in good accordance with the experimental ee values.

Keywords: NMR spectroscopy; density functional calculations; hydrogenation; iridium; reaction mechanisms.