This paper will illustrate how suitably designed phosphorus compounds enable advances in the field of (enantioselective) gold catalysis, by showcasing some of our most recent studies.<br/>The first point relates to enantioselectivity in gold catalysis. This challenging goal has been tackled notably by the design of phosphorus ligands that create extended chiral pockets reaching the coordination site opposite to phosphorus in the linear Au(I) complexes. This strategy has been typified by the design of phosphahelicenes, that is helical scaffolds terminated by phosphole units. These ligands provided excellent catalysts for a variety of gold-promoted cycloisomerization reactions. Alternatively, gold-promoted reactions can be made enantioselective by combining achiral cationic gold complexes with chiral phosphate counterions, according to the ‘Asymmetric Counterion Directed Catalysis’ approach (ACDC). The scope of ACDC has been extended successfully by a new ligand design that involves tethering of the gold complex to its phosphate counterion <i>via</i> a phosphate-functionalized phosphine. Aryl-phosphines with tethered BINOL-derived phosphate units have enabled notably highly enantioselective tandem cycloisomerization-nucleophilic additions on a-ethynyl-cyclohexenones.<br/>The second point relates to the control of the reactivity of gold complexes through external stimuli. The general aim is to change the reactivity of a given catalyst, e.g. to activate/deactivate a catalyst, by changing its structural features under the effect of light. Toward this goal, we have designed acyclic and cyclic diphosphines that display photoswitchable azobenzene units. Their E→Z photoisomerization significantly modulates the reactivity of the corresponding gold complexes.

Crossroads of gold(I) catalysis and phosphorus chemistry

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