Development of a Divergent Synthesis of Pleurotinoid Natural Products.

Herein, we describe the evolution of our syntheses of the pleurotinoid natural products pleurotin (), pleurogrisein (), and 4-hydroxypleurogrisein (). An approach based on a proximity-induced intramolecular Diels-Alder cycloaddition of a transient -quinone dimethide (e.g.

An enantiospecific synthesis of jiadifenolide.

A Robinson annulation, van Leusen homologation, and a desymmetrizing C-H oxidation enabled an enantiospecific synthesis of the neurotrophic natural product jiadifenolide. From a pulegone-derived building block, a key propellane intermediate was constructed through the use of simple reagents in a highly diastereoselective fashion. A short series of oxidations of this tricylic framework allowed progression to the natural product.