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.

The enantioselective intermolecular sp3 C–H functionalization at allylic and benzylic positions was achieved using rhodium-catalyzed reactions with 4-phenyl-N-methanesulfonyl-1,2,3-triazole. The optimum dirhodium tetracarboxylate catalyst for these reactions was Rh2(S-NTTL)4. The rhodium-bound α-imino carbene intermediates preferentially reacted with tertiary over primary C–H bonds in good yields and moderate levels of enantioselectivity (66-82% ee). This work demonstrates that N-sulfonyltriazoles can be applied to the effective C–H functionalization at sp3 C–H bonds of substrates containing additional functionality.

An efficient and convenient synthesis of 2,2,2-trichloroethyl (TCE) aryl- and vinyldiazoacetates was achieved by palladium-catalyzed cross-coupling reactions between TCE diazoacetates and aryl or vinyl iodides. The broad substrate scope allows for rapid and facile formation of TCE aryl- and vinyldiazoacetates, which recently have emerged as versatile reagents for rhodium-carbene chemistry.

A Robinson annulation, van Leusen homologation, and a desymmetrizing C-H oxidation enabled an enantiospecific synthesis of the neurotrophic natural product jiadifenolide. From a pulegonederived 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.

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