title: A hetero Diels-Alder approach to the synthesis of chromans (3,4-dihydrobenzopyrans) using oxonium ion chemistry: the oxa-Povarov reaction.
abstract: An oxa analogue of the well-known Povarov reaction has been developed for the synthesis of 3,4-dihydrobenzopyrans (chromans). The reaction involves the formal inverse electron demand [4 + 2] cycloaddition reaction of in situ-generated cationic aryl 2-oxadiene oxocarbenium ions with alkenes. The oxonium ion intermediates are generated through Lewis acid (SnCl(4))-promoted reactions of phenol-derived Rychnovsky-type mixed acetals. The yield and diastereoselectivity of the chroman products are found to depend upon the substitution pattern of the precursor alkene (i.e., monosubstituted, trans- or cis-disubstituted and cyclic alkenes). Generally, the reactions afford the endo-diastereomers as the major products, except for the reactions of trans-β-methylstyrene, which afford exo-chromans. A comparison of the product distributions from the reactions of trans- and cis-β-methylstyrene reveal that the reaction proceeds, at least in part, by a nonconcerted ionic pathway. Just as for the aza-Povarov reaction, there are two potential mechanisms for the reaction. The first mechanism involves a direct asynchronous [4 + 2] cycloaddition pathway, while the second occurs through the stepwise Prins addition of the alkene to the aryl 2-oxadiene oxonium ion, followed by an intramolecular aromatic substitution reaction of the resultant cation (i.e., a domino Prins/intramolecular Friedel-Crafts reaction).
authors.affiliation: Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, Canada, M5S 3H6.
authors.forename: Rivka R R
authors.initials: RR
authors.lastname: Taylor
authors.forename: Robert A
authors.initials: RA
authors.lastname: Batey