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Computational Mechanistic Studies of the Dearomative Intramolecular di-Dehydro Diels-Alder (IMDDA) Reactions of Ene-yne Substituted Heteroarenes

Kusevska, Elena (2020) Computational Mechanistic Studies of the Dearomative Intramolecular di-Dehydro Diels-Alder (IMDDA) Reactions of Ene-yne Substituted Heteroarenes. Master's Thesis, University of Pittsburgh. (Unpublished)

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Abstract

I have carried out density functional theory calculations on the IMMDA reactions of a series of ene-yne substituted heteroarenes, in order to understand the effects of the identity and position of substitution of the tether, the identity of the diene heteroarene, and the presence of an additional benzene ring fused to the diene heteroarene, on the mechanism and selectivity of the intramolecular Diels-Alder (DA) reaction. For a subset of these reactions, I have compared the computed free energies of reaction, the free energies of activation, and the gas phase bond-dissociation energies and acidities of DA adducts with the experimentally determined activation free energies and reaction selectivities for the final product. The results indicate that the mechanism of the DA step involves several competing pathways, including the concerted cycloadditions and the stepwise additions with either the s-cis or s-trans conformers of the ene-yne substrates. The computational studies also suggest that the product selectivity of the IMDDA reaction is under kinetic control, and that the isomerized cyclohexadiene product is most likely formed through an ionic mechanism


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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Kusevska, Elenaelk72@pitt.eduelk72
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairLiu, Peng
Committee MemberBrummond, Kay M.
Committee MemberJordan, Kenneth D.
Committee MemberJohnson, J. Karl
Date: 17 January 2020
Date Type: Publication
Defense Date: 8 May 2019
Approval Date: 17 January 2020
Submission Date: 29 August 2019
Access Restriction: 2 year -- Restrict access to University of Pittsburgh for a period of 2 years.
Number of Pages: 48
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Computational Modeling and Simulation
Degree: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: DFT mechanism IMMDDA
Date Deposited: 17 Jan 2020 13:47
Last Modified: 17 Jan 2020 13:47
URI: http://d-scholarship.pitt.edu/id/eprint/37429

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