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Pure Appl. Chem., 2011, Vol. 83, No. 9, pp. 1781-1788

Published online 2011-07-07

Straightforward synthesis of five-membered metallacycloallenes: 1-Zirconacyclopenta-2,3-diene compounds derived from 1,3-enynes

Noriyuki Suzuki1,2*, Taichiro Shimura2, Yoshio Sakaguchi1 and Yoshiro Masuyama2

1 Advanced Technology Support Division, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
2 Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-ku, Tokyo 102-8554, Japan

Abstract: A five-membered metallacycloallene complex, 1-zirconacyclopenta-2,3-diene, was prepared from low-valent zirconocene and 2,4-bis(trimethylsilyl)but-1-en-3-yne. The complex reacted with carbonyl compounds to afford alkynyl alcohols after hydrolysis via C=O insertion into Zr–C bond. Similarly, nitriles inserted into the Zr–C bond to give the corresponding ketones after hydrolysis. The insertion of C=O and CN selectively took place at zirconium-sp3 carbon of the metallacycle.