Nucleophilic carbon-carbon bond formation by 1-En-3-ynes via zirconocene-η2-1-en-3-yne complexes

•Conjugated 1-en-3-ynes reacted with low-valent zirconocene to give zirconocene-η2-1-en-3-yne complexes.•The η2-1-en-3-yne complexes reacted with ketones to give the alkynyl and allenyl alcohols after hydrolysis, and these product can be regarded as the products resulted from nucleophilic attack by the C1 atom of 1-en-3-ynes.•The η2-1-en-3-yne complexes reacted with nitriles to give the alkynyl ketones and pyrroles after hydrolysis. And they reacted with isocyanate to afford allenyl, alkynyl and dienyl amides. The distribution of the products depended on the substituents of the starting 1-en-3-ynes.•The presented method is, in principle, same as the reactivity of zirconacycloallens, which we previously reported. However, only limited number of 1-en-3-ynes can form zirconacycloallenes in good yields. Various 1-en-3-ynes can be applied for reaction by using the presented method w.