Synthesis 2004(9): 1369-1374  
DOI: 10.1055/s-2004-822398
PAPER
© Georg Thieme Verlag Stuttgart · New York

Zirconium-Mediated Intramolecular Cyclization of Yne-Imine

Muneyoshi Makabe, Yoshihiro Sato, Miwako Mori*
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
e-Mail: mori@pharm.hokudai.ac.jp;
Further Information

Publication History

Received 2 May 2004
Publication Date:
08 June 2004 (online)

Abstract

Successful zirconium-mediated intramolecular cyclization of yne-imine was achieved. When a crude imine, which was prepared from yne-aldehyde and primary amine in the presence of MgSO4, was treated with Cp2ZrBu2 at room temperature for several hours, a cyclopentane derivative was obtained in high yield. The intermediary azazirconacycle was treated with D3O+, I2 or t-BuNC to give the desired deuterated, iodinated or formylated product, respectively, at the vinyl position in good yield. Transmetalation of zirconacycle to CuCl was carried out and then allyl chloride was added to give an allylated compound in good yield. Selective bond fission of a zirconium-nitrogen bond of the azazirconacycle was achieved by treatment of the azazirconacycle with acyl halide to give an N-acylated vinylzirconium compound.