A convenient copper-catalyzed intra-/intermolecular diamination of β,γ-unsaturated hydrazones has been developed with simple amines as external amine sources. The protocol enables efficient access to various nitrogen-containing pyrazolines under mild reaction conditions.

A versatile method for the rapid synthesis of diverse functionalized pyrazolines has been developed based on copper-mediated aminofunctionalization of β,γ-unsaturated hydrazones. The scope of this strategy encompasses a range of difunctionalization reactions: aminoazidation, aminohalogenation, and aminothiocyanation. These reactions provide straightforward access to a series of useful pyrazoline building blocks containing various functional groups that are hard to access traditionally.

An efficient and step-economical copper-mediated intra-/intermolecular aminoacyloxylation of β,γ-unsaturated hydrazones has been developed. Copper carboxylates serve as both reaction promoters and carboxylate sources in these easily conducted reactions. This method provides straightforward access to diversely useful acyloxyl pyrazolines, which are hard to access traditionally, in good to excellent yields.

A novel metal‐free methodology for the synthesis of diacyl/acyl N‐allylhydrazines based on PhI(OAc)2‐promoted 1,2‐diaza‐Cope rearrangement reaction of β,γ‐unsaturated hydrazones with acetate/H2O has been described. This cascade reaction works efficiently under mild conditions. A possible mechanism involving hydrazonyl radicals and N–I(III) intermediates of β,γ‐unsaturated hydrazones is proposed.