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A Hetero Diels–Alder Approach to the Synthesis of Chromans (3,4-Dihydrobenzopyrans) Using Oxonium Ion Chemistry: The Oxa-Povarov Reaction

2012; American Chemical Society; Volume: 78; Issue: 4 Linguagem: Inglês

10.1021/jo302328s

1520-6904

Rivka R. R. Taylor, Robert A. Batey,

Synthesis of Indole Derivatives

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).