Rhodium catalyzed one-step hydroamidation of cyclopentadiene and dicyclopentadiene

Abstract

A one-step rhodium catalyzed direct route from alkene to amide is presented via the hydroamidation reaction of cyclopentadiene and dicyclopentadiene with pyrrolidine. A homogeneous catalyst of [Rh(cod)Cl]₂ without additional phosphorus ligands was established giving a 90% yield of the respective monoamide species of Dcpd with a high TOF of 1060 h⁻¹. An important side reaction in hydroamidation reactions is the formation of oligomers of dicyclopentadiene. This unwanted reaction could be overcome by the optimum adjustment of the olefin/amine ratio. The desired atom economic hydroamidation, which uses the inexpensive bulk chemicals carbon monoxide and dicyclopentadiene, could be scaled up to a multigram scale with comparable catalyst activity.