An unprecedented catalyst-dependent regioselective [3 + 2] cycloaddition of isocyanides with aryl diazonium salts is reported. 1,3-Disubstituted 1,2,4-triazoles were selectively obtained in high yield under Ag(I) catalysis, whereas 1,5disubstituted 1,2,4-triazoles were formed by Cu(II) catalysis. These catalytic methodologies provide a controlled, modular, and facile access to 1,2,4-triazole scaffolds with high efficiency, broad substrate scope, and excellent functional group compatibility.

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A silver-catalyzed cycloaromatization of 1-(2-ethynyl-phenyl)-prop-2-yn-1-ol with isocyanides efficiently provides benzo[b]fluorene and benzofuran-pyrrole derivatives through a modular cascade reaction that includes a nucleophilic attack on the diyne substrate. A CÀC cross-coupling/oxygen transportation/Diels-Alder/hydrogen shift/isomerization cascade mechanistic pathway is proposed.

A silver‐induced cycloaddition of isocyanides with acyl chlorides has been developed. This transition metal‐catalyzed strategy provides an effective and scalable approach for the formation of 2,5‐disubstituted oxazoles in good to high yields. The employed silver‐based MOF catalyst can be efficiently recycled without compromising the yield.

An interesting radical coupling reaction of aromatic aldehydes with isocyanides was disclosed for the synthesis of amides catalyzed by copper. According to the experimental results and mechanistic study, the isocyano group acted as an N1 synthon rather than exhibiting the carbene-like reactivity, exploiting a new reactivity profile of isocyanides.