Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2003, Issue 20, Pages 4059-4068Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.200300414
Keywords
cycloaddition; density functional calculations diastereoselectivity; synthetic methods
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A novel approach for exo/endo stereocontrol of intramolecular Diels-Alder reactions is described. Substrates carrying a hydroxymethyl group attached to the diene and an ester group attached to the dienophile participate in hydrogen bonding in the transition state. This non-covalent interaction causes either a significant enhancement or diminution in the observed kinetic endo/exo product ratio. Thus, the parent pentadienyl maleate 12 undergoes intramolecular Diels-Alder reaction to give an approx. 5:1 mixture of trans- and cis-fused bicyclic cycloadducts, whereas the C2-hydroxymethyl analogue 1 delivers a 1: 1 ratio of products. In contrast, the parent pentadienyl fumarate 13 gives a 3:2 trans:cis ratio, which is improved to 9:1 in the C2-hydroxymethyl analogue 4. These stereoselectivities are accurately predicted from transition structure populations calculated using B3LYP/6-31+G(d) theory. The presence of an intramolecular H-bond confers a transannular Diels-Alder-like appearance upon the transition states of these reactions. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
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