Zirconium-Mediated Intramolecular Cyclization of Yne-Imine

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.

Key words

yne-imines - cyclization - zirconium

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