Selective functionalization of ubiquitous CÀ H bonds of molecules would provide novel retrosynthetic insights and powerful tools for the rapid construction of molecular complexity. In this context, Cp*Ir(III) complexes have exhibited versatile reactivity towards the selective conversion of CÀ H bonds, with key features that include the use of readily transformable raw materials, great selectivity (chemo-, stereo-and regio-), high efficiency, mild reaction conditions and they enable late-stage modification of complex molecules. Recently, Cp*Ir(III) catalysis has achieved a broad range of reactions such as multiple dehydrogenations and stereoselective CÀ X bond formations. These advancements are valuable to organometallic chemists and enable the efficient synthesis of functionalized architectures.

Primary sulfonamides are widely used structural skeletons in bioactive molecules, however their direct modification via C–H functionalization remains to be developed.

Streamlining the generation of diverse highly functionalized molecules from abundant feedstocks holds great synthetic promises and challenges in pharmaceutical and material discovery. Herein, we report a tunable selectivity in multiple cascade reactions for the divergent assembly of fused N-heterocycles, comprising sequential activation of C–H and C–C bonds. Isolatable indene-type intermediates might be responsible for the generation of densely substituted fused pyridines, azepines, and azafluorenones products. The tolerance of strongly coordinating N-heterocycles, and those readily applicable for the late-stage modifications of pharmaceuticals and material molecules precursors, further demonstrated the synthetic robustness of this transformation.

The exploration of synthetic versatile, while weak coordinated amine derivatives enabled regioselective C‒H functionaliza-tion, remained challenging due to the elusive achievement of reactivity and selectivity simultaneously. Herein, with the assis-tance...

Medium N-heterocycles, azepines and azocines, serve as important skeletons that occurred widely in natural products, however, due to the lack of efficient synthetic methodologies, their application potential in biologically active molecules, pharmaceuticals and agrochemicals remained to be explored. In this context, rhodium catalysis in this field featured good reactivity and functional group tolerance, with readily available starting materials, and enabled rapid access to the azepines and azocines. Delightfully, great achievements in the concise construction of these 7 and 8-membered N-heterocycles under rhodium catalysis have been made, which mainly included cycloisomerization of unsaturated CÀ X bonds (which might also combine the ring-opening strategy on strained rings), metal carbenoid or nitrene insertion involved transformations and direct CÀ H activation reactions. Considering the great performance of rhodium catalyst in the synthesis of azepines and azocines, herein, we summarized the recent results in this field, and wish to give further insight and inspired more encouraging methodologies and new drug discovery based on these 7 and 8membered N-heterocycles.