Regioselectivity of radical additions to substituted alkenes: Insight from conceptual density functional theory

Freija De Vleeschouwer, Pablo Jaque, Paul Geerlings, Alejandro Toro-Labbé, Frank De Proft

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)

Abstract

(Figure presented) Radical additions to substituted alkenes are among the most important reactions in radical chemistry. Nonetheless, there is still some controversy in the literature about the factors that affect the rate and regioselectivity in these addition reactions. In this paper, the orientation of (nucleophilic) radical additions to electron-rich, -neutral, and -poor monosubstituted substrates (11 reactions in total) is investigated through the use of chemical concepts and reactivity descriptors. The regioselectivity of the addition of nucleophilic radicals on electron-rich and -neutral alkenes is thermodynamically controlled. An excellent correlation of 94% is found between the differences in activation barriers and in product stabilities (unsubstituted versus substituted site attack). Polar effects at the initial stage of the reaction play a significant role when electron-poor substrates are considered, lowering the extent of regioselectivity toward the unsubstituted sites, as predicted from the stability differences. This is nicely confirmed through an analysis for each of the 11 reactions using the spin-polarized dual descriptor, matching electrophilic and nucleophilic regions.

Original languageEnglish
Pages (from-to)4964-4974
Number of pages11
JournalJournal of Organic Chemistry
Volume75
Issue number15
DOIs
Publication statusPublished - 6 Aug 2010

ASJC Scopus subject areas

  • Organic Chemistry

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