Theoretical analysis of the high versatility in PtCl2-mediated cycloisomerization of enynes on a common mechanistic basis.

[Reaction: see text]. Transformations of enynes upon treatment with electrophilic transition-metal complexes, such as PtCl2, are strongly substrate-dependent processes and may yield a wide variety of cyclic compounds. Despite the high versatility, many of these processes could be closely related from a mechanistic point of view. Theoretical analyses of the plausible reaction mechanisms provide support for a unified mechanistic picture based on the electrophilic activation of the triple bond by the catalyst, which triggers the nucleophilic alkene attack through an endo- or exo-cyclization mode, to form the cyclopropylcarbene species. Then, these common key intermediates may evolve through alternative paths to afford a range of cyclic compounds. The preference for each path and the evolution of these intermediates are governed by the nature of the starting enyne. The effects induced by different structural motifs, such as the role played by a heteroatom directly attached to the triple bond, the tether length, the substitution on the acetylenic position, and the gem-dialkyl substitution on the tether, among others, are discussed. The proposed common mechanistic scheme can rationalize and account for the experimental observations accumulated.