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Letter

On the Endo/Exo Stereoselectivity of Intramolecular Diels−Alder Reactions of Hexadienylacrylates: An Interesting Failure of Density Functional Theory

Supporting Info

Garth A. Jones,^† Michael N. Paddon-Row,*^† Michael S. Sherburn,*^‡ and Craig I. Turner^‡

School of Chemical Sciences, University of New South Wales, Sydney, 2052, Australia, and School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia

Org. Lett., 2002, 4 (22), pp 3789–3792

DOI: 10.1021/ol0264713

Publication Date (Web): October 5, 2002

†

University of New South Wales.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

‡

University of Sydney.

, m.paddonrow@unsw.edu.au

Abstract

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.

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