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Computational design of an intramolecular frustrated Lewis pair catalyst for enantioselective hydrogenation

Sharma, Gitanjali, Newman, Paul D. ORCID:, Melen, Rebecca ORCID: and Platts, James A. ORCID: 2020. Computational design of an intramolecular frustrated Lewis pair catalyst for enantioselective hydrogenation. Journal of Theoretical and Computational Chemistry 19 , 2. 10.1142/S0219633620500091

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We report DFT calculations on potential intramolecular, enantioselective hydrogenation catalysts based around borenium-carbenes based on a camphor scaffold. Using the M06-2X meta-hybrid functional, we find frustrated Lewis pair (FLP) behaviour with suitably chosen linkers that prevent association of Lewis bases with the borenium centre. These intramolecular FLPs are predicted to be able to heterolytically dissociate H2. Barriers to dissociation and the and endo/exo-ergic nature of the reaction can be tuned by the nature of the base and substituent on B. The reactivity of the hydrogenated FLP catalyst with olefin and carbonyl substrates is then explored: we predict concerted reactions for all substrates considered with relatively low barriers and large exoergic character. Hydrogenation of both faces of a prochiral substrate is also examined, indicating a small but significant variation in reaction barrier in favour of the Si-face, ascribed to stronger interactions with the aromatic π-system in the TS compared to the Re-face.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Advanced Research Computing @ Cardiff (ARCCA)
Publisher: World Scientific Publishing
ISSN: 0219-6336
Date of First Compliant Deposit: 13 March 2020
Date of Acceptance: 3 March 2020
Last Modified: 07 Nov 2023 06:53

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