Abstract: | 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. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 816–823, May, 1998. |