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

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 k 2 were analyzed with the Mayr-Patz equation, lg k = s N(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.

SUBMITTER: Mayer RJ 

PROVIDER: S-EPMC8179571 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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

Mayer Robert J RJ   Allihn Patrick W A PWA   Hampel Nathalie N   Mayer Peter P   Sieber Stephan A SA   Ofial Armin R AR  

Chemical science 20210209 13

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 <i>k</i> <sub>2</sub> were analyzed with the Mayr-Patz equation, lg <i>k</i> = <i>s</i> <sub>N</sub>(<i>N</i> + <i>E</i>), to furnish the electrophilicity descriptors <i>E</i> for the Michael acceptors. Cyclic enones and lactones show different  ...[more]

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