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Issue 13, 2021
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Electrophilic reactivities of cyclic enones and α,β-unsaturated lactones

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Abstract

The reactivities of cyclic enones and α,β-unsaturated lactones were characterized by following the kinetics of their reactions with colored carbon-centered reference nucleophiles in DMSO at 20 °C. The experimentally determined second-order rate constants k2 were analyzed with the Mayr–Patz equation, lg k = sN(N + E), to furnish the electrophilicity descriptors E for the Michael acceptors. Cyclic enones and lactones show different reactivity trends than their acyclic analogs. While cyclization reduces the reactivity of enones slightly, α,β-unsaturated lactones are significantly more reactive Michael acceptors than analogously substituted open-chain esters. The observed reactivity trends were rationalized through quantum-chemically calculated Gibbs energy profiles (at the SMD(DMSO)/M06-2X/6-31+G(d,p) level of theory) and distortion interaction analysis for the reactions of the cyclic Michael acceptors with a sulfonium ylide. The electrophilicities of simplified electrophilic fragments reflect the general reactivity pattern of structurally more complex terpene-derived cyclic enones and sesquiterpene lactones, such as parthenolide.

Graphical abstract: Electrophilic reactivities of cyclic enones and α,β-unsaturated lactones

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Article information


Submitted
03 Dec 2020
Accepted
09 Feb 2021
First published
09 Feb 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 4850-4865
Article type
Edge Article

Electrophilic reactivities of cyclic enones and α,β-unsaturated lactones

R. J. Mayer, P. W. A. Allihn, N. Hampel, P. Mayer, S. A. Sieber and A. R. Ofial, Chem. Sci., 2021, 12, 4850
DOI: 10.1039/D0SC06628A

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