2026-08-22T19:39:10Zhttps://docta.ucm.es/rest/oai/requestoai:docta.ucm.es:20.500.14352/1092142025-03-18T11:48:44Zcom_20.500.14352_14col_20.500.14352_15
Docta Complutense
author
González Pinardo, Daniel
author
Bickelhaupt, F. Matthias
author
Fernández López, Israel
2024-10-22T10:42:51Z
2024-10-22T10:42:51Z
2024
D. González-Pinardo, F. M. Bickelhaupt and I. Fernández, Origin of the Felkin–Anh(–Eisenstein) model: a quantitative rationalization of a seminal concept, Chem. Sci., 2024, 15, 12380–12387.
10.1039/d4sc03176h
https://hdl.handle.net/20.500.14352/109214
https//doi.org/10.1039/d4sc03176h
https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03176h
Quantum chemical calculations were carried out to quantitatively understand the origin of the Felkin–Anh(–Eisenstein) model, widely used to rationalize the π-facial stereoselectivity in the nucleophilic addition reaction to carbonyl groups directly attached to a stereogenic center. To this end, the possible approaches of cyanide to both (S)-2-phenylpropanal and (S)-3-phenylbutan-2-one have been explored in detail. With the help of the activation strain model of reactivity and the energy decomposition analysis method, it is found that the preference for the Felkin–Anh addition is mainly dictated by steric factors which manifest in a less destabilizing strain-energy rather than, as traditionally considered, in a lower Pauli repulsion. In addition, other factors such as the more favorable electrostatic interactions also contribute to the preferred approach of the nucleophile. Our work, therefore, provides a different, more complete rationalization, based on quantitative analyses, of the origin of this seminal and highly useful concept in organic chemistry.
eng
Attribution 4.0 International
Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept
journal article
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GonzalezBickelhaupt_OriginoftheFelkin-Anh_2024.pdf
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https://docta.ucm.es/bitstreams/9417b2b3-896f-4be5-829f-aeec3dec3d6e/download
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text/plain
GonzalezBickelhaupt_OriginoftheFelkin-Anh_2024.pdf.txt