A First Theoretical Study on the Origin of the Metal-Mediated Regioselective Opening of 2,3-Epoxy Alcohols

Ivan Infante, Carlo Bonini, Francesco Lelj, Giuliana Righi

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Hybrid density functional theory (B3LYP) method allows the study of the role of metal ions (Li(+)) in the regioselective opening of 2,3-epoxy alcohols with lithium halides (Cl, Br, I) to the corresponding halohydrins. The theoretical results largely confirm the experimental results, especially with regards to the regioselectivity observed in the opening of the oxirane ring. The C3 halogen attack is always preferred to the C2 attack, with a significant difference in the TS structures with the reaction pathway under kinetic control. The central role of the lithium cation, linked to the oxygen atoms of the epoxy alcohol, is well documented in the reaction mechanisms presented. The energy differences between the two structures of the proposed TS appear to be ascribed to the different contribution of the X-H-O hydrogen bond between the hydroxyl groups of the reactant and the incoming halogen nucleophile.
Original languageEnglish
Pages (from-to)3773-3780
Number of pages8
JournalJournal of Organic Chemistry
Volume68
Issue number10
DOIs
Publication statusPublished - 1 May 2003
Externally publishedYes

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