This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions of C–C multiple bonds that have been realized due to the productive integration of Au(i)/Au(iii)catalysis with unique π-activation mode of gold complexes.

By adopting the interplay of ligand-enabled Au(I)/Au(III) catalysis and the unique π-activation mode of gold complexes, a highly underscored 1,2-heteroarylation of alkenes has been accomplished. The present ligand-enabled approach not...

Reported herein is the gold-catalyzed 1,2-aminoarylation of alkenes that engages external amine as a coupling partner. Careful optimization studies revealed a significant role of the concentration of base to achieve highly chemoselective access to the aminoarylation products over potential C–N cross-coupled products. Overcoming all the limitations, the current strategy provided straightforward access to the medicinally relevant 3-aminochroman, 2-aminotetra­hydro­naphthalene, and 2-aminoindane derivatives.

Gold-catalyzed diyne cycloisomerizations involving carbene/alkyne metathesis have been the focal point of attention for the past few years as it offers great potential to build complex polycyclic architectures. However, the design of novel cycloisomerizations has been mostly limited to 1,5/1,6- diynes and has remained very challenging to apply for higher 1,n-diynes. Herein, we disclose an unprecedented cycloisomerization of pyridine-bridged 1,8-diynes involving carbene/alkyne metathesis to access luminescent cycl[3.2.2]­azines.

Herein we report C­(sp2)–S cross-coupling reactions of aryl iodides and arylsulfonyl hydrazides under ligand-enabled, Au­(I)/Au­(III) redox catalysis. This strategy operates under mild reaction conditions, requires no prefunctionalized aryl coupling partner, and works across several aryl iodides. The utility of this protocol is highlighted through the synthesis of various medicinally relevant biaryl sulfones. The reaction mechanism is supported with control experiments, mass spectrometry, and NMR studies.