On the Endo/Exo stereoselectivity of intramolecular Diels-Alder reactions of hexadienylacrylates: An interesting failure of density functional theory

Garth A. Jones, Michael N. Paddon-Row, Michael S. Sherburn, Craig I. Turner

Research output: Contribution to journalArticlepeer-review

40 Citations (Scopus)


graphic A combined experimental and computational study of endo/exo stereoselectivity in a series of IMDA reactions of hexadienylacrylates has found that DFT makes erroneous predictions when the endo and exo transition states possess differing degrees of conjugation. These problems are overcome by carrying out calculations at the MP2 level of theory, which gives remarkably accurate Boltzmann distributions of products. These findings are used to predict ways to obtain either endo- or exo-cycloadducts exclusively.
Original languageEnglish
Pages (from-to)3789-3792
Number of pages4
JournalOrganic Letters
Issue number22
Publication statusPublished - 2002

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