Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

Palladium-catalyzed C-H arylation using phosphoramidate as a directing group at room temperature.

This communication describes the first phosphoramidate directing group for synthetically useful arylation. Remarkably, the nature of a new directing group drives selective C-H bond activation to afford diverse N-aryl phosphoramidates in good to excellent yields at room temperature.

A regio- and stereoselective synthesis of trisubstituted alkenes via gold(I)-catalyzed hydrophosphoryloxylation of haloalkynes.

A new stereoselective synthesis of trisubstituted alkenes is developed. Hydrophosphoryloxylation of haloalkynes provides Z-alkenyl halophosphates, which undergo Pd-catalyzed consecutive cross-coupling reactions to afford regio- and stereodefined trisubstituted alkenes.

Gold(I)-catalyzed addition of carboxylic acids to alkynes.

Au(I)-catalyzed hydroacyloxylation of alkynes with carboxylic acids is described. PPh3AuCl/AgPF6 catalyst affords the Markonikov addition products, whereas PPh3AuCl/AgOTf catalyst gives the more stable isomerized products via the Markonikov products.