A novel reaction of cycloalumination of olefins and acetylenes mediated by metallocomplex catalysts

Results obtained in the discovered by the authors catalytic cycloalumination reaction of unsaturated compounds in the presence of complex Ti- and Zr-containing catalysts are generalized. Cycloalumination of olefins and acetylenes proceeds under the action of Ti and Zr complexes in one stage to give novel classes of organoaluminum compounds (OAC): alumacyclopentanes, alumacyclopropanes, alumacyclopropenes, 1,4-dialumabutanes, and 1,2-dialumaethylenes. Based on these cyclic and acyclic OAC, essentially new preparative synthetic methods were elaborated. Novel reactions (β-ethylation, β-vinylation, reductive β-ethylation, and reductive β-vinylation) allow transforming olefins and acetylenes into fivemembered heterocycles, cyclopropanes, cyclobutanes, conjugated 1,3-dienes, primary alkyl iodides, 3-substituted alk-1-enes, andthreo-2,3-disubstituted butane-1,4-diols under mild conditions in high yields. The mechanisms of the presented reactions are discussed.