A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

Peter Brandt, Per-Ola Norrby, Ivar Martin, Tobias Rein

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The solvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate determining step was found to be the ring closure of an oxyanion to an oxaphosphetane. Solvation was found to have a drastic influence on the reaction path. In most solvated systems, the bimolecular formation of the oxyanion intermediate may be rate limiting. Previously postulated isomerization side paths were investigated. Several effects that could rationalize experimentally observed trends for (E)/(Z)-selectivities have been identified.
    Original languageEnglish
    JournalJournal of organic chemistry
    Volume63
    Pages (from-to)1280-1289
    Publication statusPublished - 1998

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