A Highly Active Hydroformylation Catalyst Using a Self‐Assembling Bis‐N‐Pyrrolyl Phosphine Ligand

Abstract

Herein we report an improved self-assembling phosphorus ligand based on hydrogen bonding between pyridone/hydroxypyridine in the ligand backbone. The Npyrrolyl substituents significantly improve the π-backbonding properties of the ligand. Rhodium, iridium and platinum complexes of the ligand were prepared and analyzed by NMR spectroscopy and x-ray crystal structure analysis. A catalyst based on this ligand showed very high catalytic activity and linear regioselectivity in rhodium-catalyzed hydroformylation of 1-octene. The same ligand was applied in linear regioselective iridium-catalyzed hydroformylation of 1-octene.

Highly (regio)selective hydroformylation of olefins using self-assembling phosphines

“…31 More recently, the groups of Reek and Breit reported further examples following this ligand design. 27,32,33…”

“…Based on our long-standing interest in carbonylation reactions and inspired by all those results, we aimed at developing new 6-DPPON analogues 33 for the rhodium hydroformylation of terminal olefins. Herein, we report the synthesis and activity assessment of several monodentate self-assembling phosphines bearing the 6-pyridinone moiety.…”