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Updated: Aug 3, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Epoxide-opening and group-transfer reactions mediated by monomeric zirconium imido complexes
Suzanne A Blum1, Patrick J Walsh, Robert G Bergman
1Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Abstract:
N-tert-Butylimidozirconocene (Cp2Zr=Nt-Bu) and its analogue (ebthi)Zr=NAr (ebthi = ethylenebis(tetrahydroindenyl), Ar = 2,6-dimethylphenyl) undergo overall cycloaddition reactions at ambient temperature with epoxides that lack accessible beta-hydrogens. The process results in addition of the Zr=N bond to an epoxide C-O bond, leading to azazirconacyclopentanes. The regio- and stereochemistry of the products implicate a stepwise mechanism, with the intermediacy of zwitterions having substantial carbocation character at the substituted carbon of the ring-opened epoxide-derived fragment. The azametallacycles undergo facile cleavage to beta-amino alcohols upon addition of mild acid.
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