The thorough understanding of a catalytic process at its molecular level uncovers the features controlling the activity, the selectivity, and the activation–deactivation pathways. Such insights enable rational development of a new generation of catalytic processes with improved performance. We consider that such an approach is particularly attractive for the advancement of well-established industrial processes that, despite their exhaustive empirical trial-and-error optimizations, still often suffer from pertinent limitations.

Pd-catalyzed hydroformylation reactions with elusive chemo- regioselectivities of industrial importance

Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>10⁷ metric tons yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Based on our exhaustive mechanistic studies of Pd-catalyzed hydrocarbonylation reactions, we developed the highly selective β-hydroformylation of functionalized alkenes and alkynes (J. Am. Chem. Soc. 2020, 142, 18251).

Based on the gained mechanistic understanding, we devised the first example of the commercially desirable but elusive isoselective hydroformylation of short-chain aliphatic alkenes, such as propylene (EP21315257 patent application; Angewandte Chemie 2022 (in press) DOI: 10.1002/anie.202116406). The technology is at the maturation stage conducted in collaboration with Conectus, a SATT, Technology Acceleration Transfer Company dedicated to collaborative research and technology transfer from public research laboratories to the market.

Pd-catalyzed hydrocarbonylation reactions

With shared mechanistic features of palladium-catalyzed hydrocarbonylation technologies, the gained knowledge into one reaction can be further capitalized to advance various other transformations. Therefore, the approach bears the potential to lift existing limitations in other industrially important carbonylation reactions, such as hydroxy-, alkoxy-, thio- and aminocarbonylation reactions, which are appealing for the synthesis of highly valuable carbonyl compounds such as carboxylic acids, esters, thioesters, or amides, used as fine chemicals and bulk materials. Our efforts are focused on establishing the full potential, the scope, and the limitations of the strategies.