Competitive Pseudopericyclic [3,3]- and [3,5]-Sigmatropic Rearrangments of Trichloroacetimidates

Shikha Sharma, Trideep Rajale, Daniel K Unruh, David Birney

Research output: Contribution to journalArticlepeer-review


The Woodward-Hoffmann rules predict whether concerted pericyclic reactions are allowed or forbidden based on the number of electrons involved and whether the cyclic orbital overlap involves suprafacial or antarafacial orbital overlap. Pseudopericyclic reactions constitute a third class of reactions in which orthogonal orbitals make them orbital symmetry allowed, regardless of the number of electrons involved in the reaction. Based on the recent report of eight-centered ester rearrangements, it would be predicted that the isoelectronic eight-centered rearrangements of imidates would also be allowed. We now report that these rearrangements occur, and indeed an eight-centered rearrangement is slightly favored in at least one case, over the well-known six-centered Overman rearrangements, in a trichloroacetimidoylcyclohexadienone, a molecular system where both rearrangements are possible.
Original languageEnglish
Pages (from-to)11734–11743
JournalJournal of Organic Chemistry
StatePublished - Aug 20 2015

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