Relativistic effects in homogeneous gold catalysis

Transition metal catalysts containing gold, especially cationic phosphine-gold(I) complexes, are emerging as powerful catalysts for a growing number of synthetic transformations. Theoretical studies on gold, particularly relativistic effects, can provide a framework for rationalizing the observed reactivity of these catalysts. David Gorin and F. Dean Toste draw on experimental and computational data to present our current understanding of homogeneous gold catalysis. Transition metal catalysts containing gold present exciting new opportunities for chemical synthesis. Experimental and computational data is reviewed to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology. 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.