Synthesis of glyco-Fused Bicyclic Compounds; Conformationally Constrained Scaffolds and Useful Polyfunctional Building Blocks

We synthesized fused bicyclic polyfunctional compounds containing a highly hydroxylated pyran ring starting from commercially available methyl glucopyranoside and adopting a RCM annulation approach. The versatile α,β‐unsaturated ketone group was introduced on the newly formed ring and, as an example of the potential of these polyfunctionalized building blocks, a tetracyclic compound was synthesized through a Diels–Alder cycloaddition reaction. Bicyclic polyfunctional glycol‐fused compounds have been synthesized from commercially available methyl gluco‐pyranoside. These molecules, with their high chirality content, presence of an α,β‐unsaturated ketone and multiple hydroxyl groups represent useful building blocks for the preparation of complex, optically pure compounds.