Gold-Catalyzed Heck Reaction

Herein, we report a gold-catalyzed Heck reaction facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis. The ele-mentary organometallic steps such as migratory insertion and β-hydride elimination have been realized in the catalytic fash-ion for the first time in gold chemistry. The present methodology not only overcomes the limitations of previously known transition metal-catalyzed Heck reactions such as the requirement of specialized substrates and formation of a mixture of regioisomeric products as a result of the undesirable chain-walking process but also offers complementary regioselectivity as compared to other transition metal catalysis

Unlocking the Chain-Walking Process in Gold Catalysis

The successful realization of gold-catalyzed chain-walking reactions, facilitated by ligand-enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough has led to the development of gold-catalyzed annulation reaction of alkenes with iodoarenes by leveraging the interplay of chain-walking and π-activation reactivity mode. The reaction mechanism has been elucidated through comprehensive experimental and computational studies

Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Rationally Designed Chiral (P,N)-Ligands

We report, for the first time, the concept of enantioselective Au(I)/Au(III) redox catalysis, enabled by the newly designed hemilabile chiral (P,N)-ligands – ChetPhos. The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to underpin the enantioinduction model, which revealed that the greater trans-influence of phosphorus allows precise positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity