Formal Synthesis of (±)-Salvinorin A via Gold(I) Catalysis.

The formal synthesis of (±)-salvinorin A is presented. Our approach utilizes two distinct gold(I) catalytic processes. The combination of a gold(I)-catalyzed reaction with an intermolecular Diels-Alder reaction followed by a gold(I)-catalyzed photoredox reaction generated in eight steps the framework of the natural product with high diastereoselectivity.

A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine.

Synthesis and Isolation of Organogold Complexes through a Controlled 1,2-Silyl Migration.

During our efforts toward the synthesis of naturally occurring polyprenylated polycyclic acylphloroglucinol using a Au(I)-catalyzed 6-endo dig carbocyclization, we isolated stable vinyllic gold intermediates. Optimization lead to isolated yields of up to 98%, using 2-(di-tert-butylphosphino)biphenyl as the ligand. This transformation is derived from a silyl rearrangement that can be fully controlled according to the nature of the substituent on the ynone.