A facile synthesis of biologically important S-aryl dithiocarbamates has been demonstrated by the aryne three-component coupling involving CS2 and aliphatic amines. This transition-metal-free and mild reaction is scalable and operates with good functional group compatibility. Preliminary mechanistic experiments, including density functional theory studies, are also provided. Moreover, with 3-triflyloxybenzynes, a unique four-component coupling incorporating tetrahydrofuran was observed.

A transition-metal-free, three-component, and diastereoselective [6 + 3] annulation reaction employing tropone, imino esters, and arynes allowing the synthesis of bridged azabicyclo[4.3.1]­decadienes is demonstrated. The key nitrogen ylides for the [6 + 3] annulation were generated by the addition of imino esters to the arynes followed by a proton transfer. The nitrogen ylides undergo a regioselective addition to tropone to furnish the desired products in moderate to good yields with good functional group tolerance under mild conditions.

Two-step, ring-opening 1,3-carbothiolation of donor–acceptor (D–A) cyclopropanes employing alkyl halides and in situ generated dithiocarbamates (from amines and CS2) has been demonstrated under mild conditions. The reaction is operationally simple and works with good functional group compatibility. Three new bonds including C–N, C–S, and C–C are formed in this 1,3-bifunctionalization strategy. Electron-poor olefins can also be used as electrophiles instead of alkyl halides. The use of enantiomerically pure D–A cyclopropane afforded enantiopure 1,3-carbothiolated product, thus demonstrating the stereospecificity of the reaction.

The use of benzotriazoles as nucleophilic triggers in the three-component Yb(OTf) 3 -catalyzed ring-opening 1,3aminofunctionalization of donor−acceptor (D−A) cyclopropanes is presented. Using N-halo succinimide (NXS) as the third component, the reaction afforded the 1,3-aminohalogenation product in up to an 84% yield. Moreover, using alkyl halides or Michael acceptors as the third components, the 3,1-carboaminated products are formed in up to a 96% yield in a one-pot operation. Employing Selectfluor as the electrophile, the reaction furnished the 1,3-aminofluorinated product in a 61% yield.

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