Diene-Transmissive Cycloadditions: Control of Monocycloaddition by Self-Assembly on a Lewis Acid Template

The sequential control of diene-transmissive Diels−Alder reactions to expand their versatility for natural product synthesis and the preparation of diversity oriented libraries is described. Self-assembly of the components (trienol 5 and methyl acrylate) via a Lewis acid template proceeds with regio-, diastereo-, and enantioselective [(S)-BINOL added] control to the monoadduct. In contrast, no cycloaddition reaction occurred at 22 °C in the absence of catalyst. This protocol obliterates the necessity of tether installation for an intramolecular cyclization.