title: Substituent-controlled reactivity in the Nazarov cyclisation of allenyl vinyl ketones.
abstract: Alkyl substitution α 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, α 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.
authors.affiliation: Department of Chemistry, Dalhousie University, Nova Scotia, B3H 4R2, Canada.
authors.forename: Vanessa M
authors.initials: VM
authors.lastname: Marx
authors.forename: Rhonda L
authors.initials: RL
authors.lastname: Stoddard
authors.forename: Gavin S
authors.initials: GS
authors.lastname: Heverly-Coulson
authors.forename: D Jean
authors.initials: DJ
authors.lastname: Burnell