Diiodomethane-Mediated Generation of N‑Aryliminium Ions and Subsequent [4 + 2] Cycloadditions with Olefins

Herein, we report a method for in situ generation of N-aryliminium ions via reactions of N,N-dimethylanilines with diiodomethane. We used the method to prepare tetrahydroquinolines via one-pot three-component reactions between N,N-dimethylanilines, diiodomethane, and olefins. This transformation inv...

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Bibliographic Details
Published in:Journal of organic chemistry 2020-02, Vol.85 (4), p.2456-2465
Main Authors: Zhao, Yu-Quan, Tian, Jun-Jie, Ai, Chong-Ren, Wang, Xiao-Chen
Format: Article
Language:English
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Summary:Herein, we report a method for in situ generation of N-aryliminium ions via reactions of N,N-dimethylanilines with diiodomethane. We used the method to prepare tetrahydroquinolines via one-pot three-component reactions between N,N-dimethylanilines, diiodomethane, and olefins. This transformation involves initial reaction of the aniline with diiodomethane to form an iodomethylammonium salt, which undergoes fragmentation accompanied by elimination of methyl iodide to give an N-aryliminium ion, which is trapped by the olefin via [4 + 2] cycloaddition to give the final product. This method for generating N-aryliminium ions requires neither a catalyst nor a strong oxidant, suggesting that it can be expected to find broad utility, especially for substrates that are sensitive to Lewis acids, transition metals, or strong oxidants.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b03148