A detailed mechanism of allene formation via the ZnI₂-promoted alleylation of terminal alkynes (ATA reaction) was investigated through DFT. The originally proposed pathway for this process was evaluated and accords perfectly with the calculated results. The formation of a propargylamine, the subsequent [1,5]-hydride migration, and β-elimination are the key steps of the whole process. The [1,5]-hydride migration is the rate-determining step. The main role of ZnI₂ in the whole process is alkyne activation to facilitate the [1,5]-hydride migration and the stabilization of the zwitterionic intermediate.

The [PtCl₂]- or [AuCl]-catalyzed reaction of 1-(indol-2-yl)-2,3-allenols occurred smoothly at room temperature to afford a series of poly-substituted carbazoles efficiently. Compared with the [PtCl₂]-catalyzed process, the [AuCl]-catalyzed reaction represents a significant advance in terms of the scope and the selectivity. Selective 1,2-alkyl or aryl migration of the gold carbene intermediate was observed: compared with the methyl group, the isopropyl, cyclopropyl, cyclobutyl, and cyclohexyl groups migrate exclusively; the cyclopropyl group shifts selectively over the ethyl group; the 1,2-migration of a non-methyl linear alkyl is faster than methyl group; the phenyl group migrates exclusively over methyl or ethyl group. DFT calculations show that water makes the elimination of H₂O facile requiring a much lower energy and validates the migratory preferences of different alkyl or phenyl groups observed.

A novel copper-catalyzed, highly regio- and stereoselective borylcupration of substituted 2,3-allenamides with bis(pinacolato)diboron producing Z-β-borylated β,γ-unsaturated enoamides has been demonstrated. Due to the unique effect of the amide-group, perfect regio- and stereoselectivity and good to excellent yields have been achieved, which were rationalized by a DFT study.