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Updated: Apr 17, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Highly selective copper-catalyzed asymmetric [3+2] cycloaddition of azomethine ylides with acyclic 1,3-dienes
María González-Esguevillas1, Ana Pascual-Escudero, Javier Adrio
1Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco 28049 Madrid (Spain), Fax: (+34) 914973966.
Abstract:
The first examples of the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with acyclic activated 1,3-dienes (and 1,3-enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ-C=C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6-addition product is detected, suggesting a stepwise mechanism. The resulting C4-alkenyl-substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3-b]pyrrole and the tetracyclic core of the alkaloid gracilamine.
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