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Abstract
Hyperconjugation/conjugation through-bond stereoelectronic effects were studied with density functional theory (DFT) in the context of 3-azabicyclo[3.3.1]nonanes to unravel puzzling differences in reactivity between a vinylogous chloride (4) and a vinylogous ester (5). These compounds—whose structures differ only by one substituent—were found to display strikingly different reactivities in hydrochloric acid by Risch and co-workers (J. Am. Chem. Soc. 1991, 113, 9411–9412). Computational analyses of substituent effects, noncovalent interactions, natural bond orbitals, isodesmic reactions, and hydration propensities lead to a model for which the role of remote, through-bond stereoelectronic effects is key to explaining 4 and 5’s diverging reactivity.
Supplementary materials
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Supporting Information
Description
Supporting Data and Figures; Energies and Frequencies of Computed Structures (PDF).
A data set collection of computational results, including geometries and structure coordinates, is available in the ioChem-BD repository and can be accessed via https://doi.org/10.19061/iochem-bd-6-120
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Supplementary weblinks
Title
Coordinates of Computed Structures
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Supporting Information data set on ioChem-BD repository.
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