Application of an Enyne Metathesis/Diels–Alder Cycloaddition Sequence: A New Versatile Approach to the Syntheses of C‐Aryl Glycosides and Spiro‐C‐Aryl Glycosides

An efficient approach for the synthesis of a variety of C‐aryl and spiro‐C‐aryl glycosides is described. This diversity‐oriented strategy employed here relies on a sequential enyne metathesis to generate the 1,3‐diene moiety and Diels–Alder reaction with different dienophiles followed by aromatisation. Whereas cross‐enyne metathesis with ethylene gas is used to install the 1,3‐diene moiety at the anomeric centre for the synthesis of C‐aryl glycosides, an intramolecular enyne metathesis on the sugar enyne is performed to generate the 1,3‐diene moiety for the synthesis of spiro‐C‐aryl glycosides. Efforts to extend this strategy to the synthesis of the core structure of natural C‐aryl glycoside gilvocarcin are also described. A combination of both C‐aryl and spiro‐C‐aryl glycosides in the same moiety to combine the features thereof has also been accomplished. A tandem enyne metathesis/Diels–Alder reaction/aromatisation has also been attempted to directly access the C‐aryl glycosides in one pot albeit in low yield.