Iridium(III) Catalysts with an Amide‐Pendant Cyclopentadienyl Ligand: Double Aromatic Homologation Reactions of Benzamides by Fourfold C−H Activation

Abstract

The synthesis, characterization, and catalytic performance of iridium(III) catalysts that bear an amide‐pendant cyclopentadienyl ligand ([CpAIrI2]2) is reported. These [CpAIrI2]2 catalysts were obtained from the complexation of a CpA ligand precursor with [Ir(cod)OAc]2 followed by oxidation. Double aromatic homologation reactions of benzamides with alkynes by fourfold C−H activation proceeded in good to high yield with these [CpAIrI2]2 catalysts, demonstrating their superior catalytic performance in this challenging transformation.

Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization

“…In this regard, the groups of Ackermann 30 , Matsunaga 31-34 , Cramer 27-29 , and Shi 35-37 independently reported Co-catalyzed asymmetric aryl C-H functionalization with unactivated olefins, maleimides or dioxazolones. Previously, the modifications of the Cp ring have resulted in an extensive array of Cp-metal catalysts [38][39][40][41][42][43][44] . However, whether the use of chiral Cp ligands in Co-catalyzed C-H functionalization reactions can influence the reaction outcomes of beyond enantioselectivity remains underdeveloped 13,[27][28][29]45,46 .Asymmetric ring-opening (ARO) of strained bicyclic olefins is an important platform for building-up molecular complexity (Fig.…”