Electrocatalytic Access to Azetidines via Intramolecular Allylic Hydroamination: Scrutinizing Key Oxidation Steps through Electrochemical Kinetic Analysis

Steve H. Park, Geunsu Bae, Ahhyeon Choi, Suyeon Shin, Kwangmin Shin, Chang Hyuck Choi, Hyunwoo Kim

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

Azetidines are prominent structural scaffolds in bioactive molecules, medicinal chemistry, and ligand design for transition metals. However, state-of-the-art methods cannot be applied to intramolecular hydroamination of allylic amine derivatives despite their underlying potential as one of the most prevalent synthetic precursors to azetidines. Herein, we report an electrocatalytic method for intramolecular hydroamination of allylic sulfonamides to access azetidines for the first time. The merger of cobalt catalysis and electricity enables the regioselective generation of key carbocationic intermediates, which could directly undergo intramolecular C-N bond formation. The mechanistic investigations including electrochemical kinetic analysis suggest that either the catalyst regeneration by nucleophilic cyclization or the second electrochemical oxidation to access the carbocationic intermediate is involved in the rate-determining step (RDS) of our electrochemical protocol and highlight the ability of electrochemistry in providing ideal means to mediate catalyst oxidation.

Original languageEnglish
Pages (from-to)15360-15369
Number of pages10
JournalJournal of the American Chemical Society
Volume145
Issue number28
DOIs
StatePublished - 19 Jul 2023

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.

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