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Combining DFT and experimental studies in enantioselective catalysis: From rationalization to prediction

Publicat a:Advances In Catalysis. 75 23-54 - 2024-01-01 75(), DOI: 10.1016/bs.acat.2024.08.002

Autors: Biosca M; Besora M; Maseras F; Pàmies O; Diéguez M

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Asymmetric catalysis is key for the achievement of important chemical products with application in the pharmaceutical and agrochemical industry. Among the various types of asymmetric catalyzed reactions, metal-catalyzed reactions are widely employed, with a diverse range of chiral catalysts available nowadays. Chiral catalysts play a crucial role in chirality induction during the formation of new bonds. Despite this diversity, certain reactions still need the development of new catalysts to enhance reactivities and selectivities of specific substrates. Nevertheless, the pursuit of these optimal catalytic systems often presents major challenges, demanding significant time and resources. The key of enantioselectivity control lies in the lowest energy transition states of the enantioselective-determining step, and will dictate the stereochemical outcome of the reaction. Although repulsive steric factors have traditionally accounted for the stability of these transition states, modern understanding includes the role of attractive forces, such as weak non-covalent interactions. Current computational methods, such as density functional theory calculations (DFT) can be applied to large systems, enabling the analysis of both factors, enhancing our comprehension of stereoselectivity origins. In this chapter, we present several illustrative examples from our recent research, using DFT calculations to elucidate the underlying factors behind enantioselectivity. Our focus was on two specific asymmetric metal-catalyzed reactions: Ir-hydrogenation of non-chelating olefins and Pd-allylic substitution. Our investigations provided new insights into the factors governing the enantioselectivity of these reactions with various chiral catalysts including P,N- and P,S-based ligands. In some cases, our findings have allowed for the prediction of catalyst enantioselectivities before their synthesis, thereby accelerating the catalyst design process.

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