LAUSR

Abstract Five-membered metallacycloallene compounds, 1-zirconacyclopenta-2,3-dienes 1, derived from but-1-en-3-ynes 2 and low-valent zirconocene, reacted with esters and isocyanates. Reactions of 1 with carboxylic esters such as ethyl acetate and methyl benzoate resulted in the formation of alkynyl ketones after hydrolysis, albeit in low yields, and diethyl carbonate gave alkynyl esters in moderate yields. Insertion of isocyanates such as phenylisocyanate to the Zr–C bond of 1 afforded an alkynyl amide when 1 had substituents at the 2,4-positions (1a), while the zirconium complexes 1 that had silyl groups at the 2,5-positions, 1b and 1c, gave dienyl amides after hydrolysis. These reactions involved C =O insertion into the Zr-Csp3 bond in 1. It is likely that the insertion afforded seven-membered 1-oxa-2-zirconacyclohepta-3,4-diene intermediates first, whilst the reaction of 2,5-disilyl-1-zirconacyclopenta-2,3-dienes 1b-c with isocyanates formed five-membered 1-oxa-2-zirconacyclopent-3-ene intermediates. Additional C–C bond formation reactions of these intermediates via transmetallation to copper salts followed by addition of allyl halides furnished allylated products.