Reported herein is the pyrazole‐directed iridium‐catalyzed enantioselective borylation of unbiased methylene C−H bonds at the position β to a nitrogen center. The combination of a chiral bidentate boryl ligand, iridium precursor, and pyrazole directing group was responsible for the high regio‐ and enantioselectivity observed. The method tolerated a vast array of functional groups to afford the corresponding C(sp3)−H functionalization products with good to excellent enantioselectivity.

The C2-selective C–H alkoxycarbonylation of indoles with alcohols and CO catalyzed by RhCl3·3H2O is disclosed that offers convenient access to diverse indole-2-carboxylic esters. The rhodium-based catalysts outperformed all other precious-metal catalysts investigated. In addition, this protocal was found applicable to the synthesis of pyrrole-2-carboxylic esters, and allowed the C–H alkoxycarbonylation in an intramolecular fashion. Preliminary mechanistic studies indicate that C–H cleavage is not likely involved in the rate-determining step, and a five-membered rhodacycle might be an intermediate involved in the reaction.