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Unveiling the Delicate Balance of Steric and Dispersion Interactions in Organocatalysis Using High-Level Computational Methods

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Yepes,  Diana
Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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List,  Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Bistoni,  Giovanni
Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Yepes, D., Neese, F., List, B., & Bistoni, G. (2020). Unveiling the Delicate Balance of Steric and Dispersion Interactions in Organocatalysis Using High-Level Computational Methods. Journal of the American Chemical Society, 142(7), 3613-3625. doi:10.1021/jacs.9b13725.


Cite as: http://hdl.handle.net/21.11116/0000-0006-03A4-D
Abstract
High-level quantum electronic structure calculations are used to provide a deep insight into the mechanism and stereocontrolling factors of two recently developed catalytic asymmetric Diels–Alder (DA) reactions of cinnamate esters with cyclopentadiene. The reactions employ two structurally and electronically very different in situ silylated enantiopure Lewis acid organocatalysts: i.e., binaphthyl-allyl-tetrasulfone (BALT) and imidodiphosphorimidate (IDPi). Each of these catalysts activates only specific substrates in an enantioselective fashion. Emphasis is placed on identifying and quantifying the key noncovalent interactions responsible for the selectivity of these transformations, with the final aim of aiding in the development of designing principles for catalysts with a broader scope. Our results shed light into the mechanism through which the catalyst architecture determines the selectivity of these transformations via a delicate balance of dispersion and steric interactions.