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Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins
- Source :
- RUA. Repositorio Institucional de la Universidad de Alicante, Universidad de Alicante (UA)
- Publication Year :
- 2021
- Publisher :
- American Chemical Society, 2021.
-
Abstract
- In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%). We gratefully acknowledge financial support from the Spanish Ministry of Science and Innovation (PID2019-104904GB-I00, PGC2018-100780-B-I00, and PGC2018-096616-B-I00), European Regional Development Fund (AEI/FEDER, UE), the Catalan Government (2017SGR1472), and the University of Alicante (VOGROB-316FI). M.B. also thanks the URV for generous support.
- Subjects :
- Government
Chemistry
Organic Chemistry
Asymmetric hydrogenation
European Regional Development Fund
Financial system
language.human_language
Olefins
Inorganic Chemistry
Química Orgánica
Ir/P,S-catalysts
language
Density functional theory
Christian ministry
Catalan
Physical and Theoretical Chemistry
Density Functional Theory
Subjects
Details
- Language :
- English
- ISSN :
- 20191049
- Database :
- OpenAIRE
- Journal :
- RUA. Repositorio Institucional de la Universidad de Alicante, Universidad de Alicante (UA)
- Accession number :
- edsair.doi.dedup.....a2b8f9fc03685327c3c5b57be4b2bb71