Hydroformylation

Abstract Hydroformylation is one of the most important homogeneously catalyzed reactions on an industrial scale. The manufacture of bulk chemicals clearly dominates. Large cobalt- and rhodium-based processes are mature technologies that have been developed over the past 80 years. Meanwhile, the potential of hydroformylation for the production of fine chemicals (perfumes, pharmaceuticals) has also been recognized. This review gives insight into the state-of-the-art of the reaction and its development. It commences with some remarks on the accidental discovery by the German chemist Otto Roelen within the historical and personal framework of the Fischer–Tropsch process, followed by the mechanistic basics of the catalytic cycle, metals used for the catalyst as well as their organic ligands. In addition, the stability of ligands and catalysts is addressed. The huge potential of this transformation is demonstrated using a variety of substrates. Finally, the use of some surrogates for syngas is discussed.