Catalysis for Total Synthesis: A Personal Account

Transition-metal catalysts containing gold present new opportunities for chemical synthesis, and it is therefore not surprising that these complexes are beginning to capture the attention of the chemical community. Cationic phosphine-gold(i) complexes are especially versatile and selective catalysts for a growing number of synthetic transformations. The reactivity of these species can be understood in the context of theoretical studies on gold; relativistic effects are especially helpful in rationalizing the reaction manifolds available to gold catalysts. This Review draws on experimental and computational data to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.

This critical review intends to familiarize the reader with the essence of pi-acid catalysis, in particular with reactions or reaction cascades effected by gold and platinum complexes. Even though materialized in apparently different reactivity modes, such noble metal catalyzed processes can be easily rationalized on the basis of a uniform mechanistic scheme that is outlined in detail. The resulting increase in molecular complexity is illustrated by selected natural product total syntheses and the formation of various intricate non-natural compounds (106 references).