An Fe(3)O(4) nanoparticle-supported copper(I) pybox catalyst, which exhibits excellent reactivity and yields products with good enantioselectivity, was developed. As a proof of concept, six optically active propargyl amines were obtained in excellent yields. The catalyst can be magnetically removed and recycled easily six times without a decrease in activity or enantioselectivity.

A metal‐free oxidative decarbonylative coupling of aliphatic aldehydes with various electron‐deficient heterocycles has been developed. This reaction is supposed to be realized via a Minisci‐type mechanism, based on the substrate scope, regioselectivity and radical trapping experiments. The ready availability of aliphatic aldehydes, metal‐free conditions and broad substrate scope should make this method attractive for the late‐stage alkylation of bioactive heterocycles.

A novel Pd(II) catalyzed direct oxidative Heck-Cassar-Sonogashira type alkynylation of indoles with terminal alkynes under an atmosphere of O(2) is developed. Unlike previous methods, the reaction does not require the pregeneration of indolyl halide or alkynyl halide. Furthermore, only a catalytic amount of base is required and oxygen was used as the ultimate "green" terminal oxidant.

An electrophilic amidation via a cationic rhodium(III)‐catalyzed C(sp2)H activation has been developed with the commercially available N‐fluorobenzenesulfonimide as the amino source under external oxidant‐free conditions. This amidation requires only a catalytic amount of base and exhibits excellent functional group tolerance and regioselectivity, providing a new avenue in direct C(sp2)H amidation.