Cyclometallated complexes as catalysts for C-H activation and functionalization.

The development of novel catalysts for C-H activation reactions with increased reactivity and improved selectivities has been attracting significant interest over the last two decades. More recently, promising results have been developed using tridentate pincer ligands, which form a stable C-M bond. Furthermore, based on mechanistic studies, the unique catalytic role of some metallacyclic intermediate species has been revealed. These experimental observations have subsequently translated into the rational design of advanced C-H activation catalysts in both Ru- and Ir-based systems. Recent breakthroughs in the field of C-H activation catalysed by metallacyclic intermediates are thus discussed.

Sulfonyl Group Dance: A Tool for the Synthesis of 6-Azido-2-sulfonylpurine Derivatives.

9-Substituted 2-chloro-6-sulfonylpurines provide 6-azido-2-sulfonylpurine derivatives with 61-83% yields when treated with sodium azide. Under optimized reaction conditions, the title compounds are obtained in a one-pot process, which involves a sequential treatment of 2,6-dichloropurines with a selected sodium sulfinate and sodium azide. Such a sulfonyl group dance (functional group swap) results from a cascade of SNAr reactions, which are facilitated by azidoazomethine-tetrazole (azide-tetrazole) tautomeric equilibrium. The formation of Meisenheimer-type intermediates as tetrazolopurine tautomers was supported by various spectroscopic methods, including 15N NMR.