Theoretical study on the mechanism of the [2 + 1] thermal cycloaddition between alkenes and stable singlet (phosphino)(silyl)carbenes

Begona Lecea, Mirari Ayerbe, Ana Arrieta, Fernando P. Cossío, Vicenç Branchadell, Rosa M. Ortuño, Antoine Baceiredo

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26 Citations (Scopus)

Abstract

The mechanism and the origins of the stereocontrol observed in the reaction between differently substituted alkenes and stable (phosphino)(silyl)carbenes giving cyclopropanes have been studied computationally. These cyclopropanation reactions proceed via asynchronous concerted mechanisms involving early transition structures with a significant charge transfer from the carbene to the alkene moiety. The geometric features of these transition structures preclude a significant overlap between the orbitals required for secondary orbital interactions between the reactants. The stereoselectivity observed experimentally stems from favorable electrostatic and steric interactions between the reactants leading to the stereoisomers in which the phosphanyl and carbonyl or aryl groups are cis to each other. © 2007 American Chemical Society.
Original languageEnglish
Pages (from-to)357-366
JournalJournal of Organic Chemistry
Volume72
Issue number2
DOIs
Publication statusPublished - 19 Jan 2007

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