The Cp2ZrCl2‐catalyzed reaction of 1‐alkynyldiphenylphosphines with Et3Al, followed by deuterolysis and oxidation, affords substituted (E)‐(but‐1‐en‐1‐yl‐1,4‐d2)diphenylphosphine oxides. It is suggested that the reaction proceeds through the formation of intermediate aluminacyclopent‐2‐enes. Substituted (E)‐but‐1‐en‐1‐yldiphenylphosphine sulfides and 4‐butyl‐5‐(diphenylphosphoryl)‐1‐phenyl‐2,3‐dihydrophosphole 1‐oxide were prepared by reacting intermediate organoaluminum compounds with S8 and PhPCl2. The mechanism of the cycloalumination of 1‐alkynylphosphines is proposed.

The interaction of 1-alkynyl phosphine oxides, sulfides, and selenides with Me 3 Al and Et 3 Al under zirconocene catalysis was studied. It has been found that the pathway of the reaction of 1-alkynyl phosphine derivatives with Et 3 Al strongly depends on the nature of the substrate and the solvent. The ethylalumination takes place in the case of 1-alkynyl phosphine oxides in hexane solvent. The reaction of 1-hexynyl phosphine oxide with Et 3 Al failed when dichloromethane was used as a solvent. Zirconium-catalyzed reaction of 1-heptynyl phosphine sulfide with Et 3 Al proceeds as the cycloalumination followed by the desulfurization under the action of low-valent zirconium complexes. 1-Heptynyl phosphine selenide was subjected to full deselenation under the reaction conditions.

The unusual transformation of N-isoalkyl-substituted propargylamines into alkenylamines under the action of Cp2ZrCl2 and organoaluminum compounds (Me3Al, EtAlCl2) has been observed. The proposed mechanism, involving the N-isoalkyl-substituted propargylamine undergoing zirconocene-initiated intramolecular hydride transfer was supported by B3LYP/6-31G(d)/LanL2DZ calculations.

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A Route to 1-Alkenylphosphine Derivatives via the Zr-Catalyzed Reaction of 1-Alkynylphosphines with Triethylaluminum. -The title reaction under conditions A) produces organoaluminum intermediates (III). They are elaborated to different interesting derivatives including the phosphole (VIII) as a potential bidentate organophosphorus ligand. -(RAMAZANOV*, I. R.; KADIKOVA, R. N.; SAITOVA, Z. R.; DZHEMILEV, U. M.; Asian J.