Goldilocks Catalysts: Computational Insights into the Role of the 3,3′ Substituents on the Selectivity of BINOL-Derived Phosphoric Acid CatalystsReportar como inadecuado


Goldilocks Catalysts: Computational Insights into the Role of the 3,3′ Substituents on the Selectivity of BINOL-Derived Phosphoric Acid Catalysts


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Publication Date: 2016-05-26

Journal Title: Journal of the American Chemical Society

Publisher: American Chemical Society

Volume: 138

Issue: 25

Pages: 7910-7917

Language: English

Type: Article

This Version: VoR

Metadata: Show full item record

Citation: Reid, J. P., & Goodman, J. M. (2016). Goldilocks Catalysts: Computational Insights into the Role of the 3,3′ Substituents on the Selectivity of BINOL-Derived Phosphoric Acid Catalysts. Journal of the American Chemical Society, 138 (25), 7910-7917. https://doi.org/10.1021/jacs.6b02825

Description: This is the final version of the article. It first appeared from the American Chemical Society via https://doi.org/ 10.1021/jacs.6b02825

Abstract: BINOL-derived phosphoric acids provide effective asymmetric catalysis for many organic reactions. Catalysts based on this scaffold show a large structural diversity, especially in the 3,3′ substituents, and little is known about the molecular requirements for high selectivity. As a result, selection of the best catalyst for a particular transformation requires a trial and error screening process, as the size of the 3,3′ substituents is not simply related to their efficacy: the right choice is neither too large nor too small. We have developed an approach to identify and quantify structural features on the catalyst that determine selectivity. We show that the application of quantitative steric parameters (a new measure, AREA(θ), and rotation barrier) to an imine hydrogenation reaction allows the identification of catalyst features necessary for efficient stereoinduction, validated by QM/MM hybrid calculations.

Sponsorship: We thank EPSRC for funding.

Embargo Lift Date: 2100-01-01

Identifiers:

External DOI: https://doi.org/10.1021/jacs.6b02825

This record's URL: https://www.repository.cam.ac.uk/handle/1810/256451



Rights: Attribution 4.0 International

Licence URL: http://creativecommons.org/licenses/by/4.0/





Autor: Reid, Jolene P.Goodman, Jonathan M.

Fuente: https://www.repository.cam.ac.uk/handle/1810/256451



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