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Updated: Apr 16, 2026

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Unusual 1,2-aryl migration in Pd(ii)-catalyzed aza-Wacker-type cyclization of 2-alkenylanilines
1Center for New Directions in Organic Synthesis, Department of Chemistry and Research Institute for Natural Sciences, Hanyang University, Seoul 133-791, Korea. sowony73@hanyang.ac.kr.
Abstract:
Inspired by the Hegedus aza-Wacker indole synthesis, we were intrigued with the fate of the aminopalladation intermediate if syn β-hydrogen is made inaccessible or unavailable. In contrast to our previously reported β-carbon elimination, cyclization of a variety of 2-alkenylaniline substrates under electrophilic palladium conditions unexpectedly afforded C3-substituted indoles. This unusual 1,2-migratory process was found to be operative across a variety of substrates with predictable migratory aptitude. A mechanistic proposal was put forward to rationalize the observed substrate dependence, and this unexpected finding could provide an opportunity for other related processes.
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