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.

Chitosan‐Silica as a Cheap Carrier and Green Soft Ligand for Improved Ru‐catalyzed Hydroformylation

“…In addition, the activity of two catalytic systems comprised of Ru 3 (CO) 12 and two well-known typical phosphines such as PPh 3 and Xantphos commonly used in hydroformylations (entries 2 and 3, Table 1), were compared with that of 0.5RuÀ Ch@SiO 2 . [50] We obtained that the influence of both phosphines on the catalytic performance of Ru 3 (CO) 12 was of the same order as with separately added Ch@SiO 2 (entry 6, Table 1) and markedly lower than that of the as-prepared 0.5RuÀ Ch@SiO 2 catalyst (entry 7, Table 1).…”

Understanding Rh‐catalysed Hydroformylation with Phosphite Ligands through Catalyst Speciation Analysis by Operando FlowNMR Spectroscopy

“…With hydroformylation kinetics generally having a negative order in CO due to competitive binding, [32–34] the use of electron‐withdrawing phosphite ligands that facilitate CO dissociation from the metal lead to increased reaction rates compared to electron‐donating ligands such as phosphines [3] . Phosphites also tend to be more stable towards aerobic oxidation than the more electron‐rich phosphines but often suffer from hydrolysis, which can be diminished by the incorporation of bulky groups in the organic backbone close to the P−O bond [3,5] . The use of sterically demanding substituents has the additional advantages of enhancing catalyst activity, as there is less space for more ligands to coordinate to Rh which allows the hydroformylation of less reactive olefins [35] .…”

“…The hydroformylation of olefins [1,2] is one of the most widely used homogeneous catalysed reactions with >10 million metric tonnes of aldehydes produced in 2008 [3–12] . Several transition metals such as Ir, Rh, Co, Ru, Fe and Pd have been used to catalyse this reaction, but only Co and Rh are used on an industrial scale due to their high activity and selectivity [3,8,13,14] .…”

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

“…In particular, rhodium(I) complexes modified with bulky aryl monophosphite ligands were found to lead to highly active, chemo- and regioselective catalysts in the hydroformylation of disubstituted and internal double bounds, under relatively mild conditions [ 14 , 15 , 16 ]. This exceptional activity results from both electronic and stereo effects: on one hand, the π-acidic character of the phosphite weakens the metal-CO bond, thereby allowing a faster CO dissociation; on the other hand, the ligand’s large cone angle allows the coordination of only one phosphite to the metal centre, even when used in large excess, which results in a low global steric hindrance around the metal centre [ 17 , 18 ]. Moreover, the design and synthesis of chiral phosphite ligands also play a key role in the development of asymmetric catalysis [ 19 , 20 , 21 , 22 ].…”