Reductive hydroformylation processes using rhodium/amine catalytic systems: scope, challenges and opportunities

This review provides a detailed and critical analysis of reductive hydroformylation catalyzed by rhodium–amine complexes under CO/H 2 pressure. It covers key developments since its discovery, insights into its mechanisms, strategies for recycling catalysts, and current challenges along with future perspectives. Special attention is given to the application of this reaction to renewable raw materials, highlighting its potential for producing high value alcohols. All these studies show that the rhodium-amine based catalytic systems exhibit excellent activity and chemoselectivity across a wide variety of substrates. However, achieving high regioselectivity – i.e. controlling the precise location at which the hydroxymethyl group attaches to the carbon–carbon double bond – remains a significant challenge with these catalytic systems. This limitation hinders the selective formation of linear alcohols from α-olefins, reducing the applicability of the reaction. Various rhodium species, whether coordinated with amine ligands or not, can participate in the catalytic process, and their involvement is highly dependent on the experimental conditions. This inherent complexity often compromises the efficient recycling of the catalytic system, thereby limiting the scalability of this technology. • Rhodium–amine catalysts enable an efficient, one-pot tandem reductive hydroformylation. • High activity and chemoselectivity are observed across various substrates. • Vegetable oil derivatives provide renewable polyols for advanced materials. • Several rhodium species may coexist and contribute to catalysis, depending on the conditions. • Catalyst recycling remains a major challenge.