Conformational control of selectivity in the dienone–phenol rearrangement

This Letter describes a series of dienone–phenol rearrangements where selectivity can be correlated with the relative stability of cationic intermediates. We have explored the dienone–phenol rearrangement of substrates where: only the p-cresol pathway is possible and relative migratory aptitudes sho...

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Bibliographic Details
Published inTetrahedron letters Vol. 48; no. 37; pp. 6590 - 6593
Main Authors Sauer, Anne M., Crowe, William E., Henderson, Gregg, Laine, Roger A.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 10.09.2007
Elsevier
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
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Summary:This Letter describes a series of dienone–phenol rearrangements where selectivity can be correlated with the relative stability of cationic intermediates. We have explored the dienone–phenol rearrangement of substrates where: only the p-cresol pathway is possible and relative migratory aptitudes should play no role in determining the regiochemistry of the reaction. For these substrates the selectivity of the rearrangement was found to depend on the stereochemistry of the spirocyclic intermediate formed during the course of the rearrangement. Rearrangement of one of these substrates gave—surprisingly—a single regioisomeric product. Selectivity in this case can be correlated with the relative stability of cationic intermediates, which lie on the pathway between spirocycle and final product.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2007.07.001