Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 29, Pages 8098-8104Publisher
WILEY-BLACKWELL
DOI: 10.1002/chem.201100519
Keywords
allenes; carbocations; cyclic compounds; cycloaddition; Nazarov reaction
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Funding
- Natural Sciences and Engineering Research Council of Canada
- Killam Trusts
- Dalhousie University
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Alkyl substitution a to the ketone of an allenyl vinyl ketone enhances Nazarov reactivity by inhibiting alternative pathways involving the allene moiety and through electron donation and/or steric hindrance. This substitution pattern also accelerates Nazarov cyclisation by increasing the population of the reactive conformer and by stabilising the oxyallyl cation intermediate. Furthermore, alpha substitution by an alkyl group does not alter the regioselectivity of interrupted Nazarov reactions when the oxyallyl cation intermediate is intercepted by addition of an oxygen nucleophile, or by [4+3] cyclisation with acyclic dienes. The regioselectivity of the Nazarov process for allenyl vinyl ketones was determined to be a result of an electronic bias in the oxyallyl cation intermediate. Computational data are consistent with this observation.
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