An efficient regioselective synthesis of 2-acylpyrroles via palladium-catalyzed addition of pyrroles with benzonitriles and subsequent hydrolysis is developed. The direct acylation reaction of protected as well as (NH)-free pyrroles proceeded smoothly to afford 2-acylpyrrole scaffolds of high biological interest.

A regioselective direct alkylation of coumarins at C-3 via cross-dehydrogenative coupling of unactivated Csp2-Csp3 bonds is developed. This protocol employs tert-butyl hydroperoxide as the sole reagent of the reaction to combine coumarins and ethers in reasonable yields under metal- and solvent-free reaction conditions. This protocol also worked well with coumarin-3-carboxylic acids to unveil a rare instance of a catalyst-free tandem alkylation/decarboxylation reaction with conservation of the double bond.

A metal-free direct alkylation of coumarins using carboxylic acids in aqueous media with a broad substrate scope is devised.

The Pd‐catalyzed reaction of pyrrole (VI) and N‐alkylated pyrroles (I) and (IV) with benzyl‐ and arylnitriles (II) gives the 2‐acylated pyrroles (III), (V), and (VII) regioselectively.