Desulfonylative Radical Truce–Smiles Rearrangement Utilizing the Benzimidazoline and Benzimidazolium Redox Couple

Ryo Miyajima; Manon Okamura; Kazuki Oomori; Hajime Iwamoto; Kan Wakamatsu; Eietsu Hasegawa

doi:10.1055/a-2153-6594

Synlett, Table of Contents

Synlett 2024; 35(03): 352-356
DOI: 10.1055/a-2153-6594

cluster

Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations

Desulfonylative Radical Truce–Smiles Rearrangement Utilizing the Benzimidazoline and Benzimidazolium Redox Couple

Ryo Miyajima

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

,

Manon Okamura

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

,

Kazuki Oomori

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

,

Hajime Iwamoto

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

,

Kan Wakamatsu

^bDepartment of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan

,

Eietsu Hasegawa∗

^aDepartment of Chemistry, Faculty of Science, Niigata University, 8050 Ikarashi-2, Nishi-ku, Niigata 950-2181, Japan

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Abstract

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This letter is dedicated to Professor Dennis P. Curran (University of Pittsburgh), who is a distinguished chemist for synthetic application of free radical chemistry, on the occasion of his Koki anniversary (70^th birthday).

Abstract

We have developed protocols for promoting redox reactions utilizing the 2-substituted 1,3-dimethylbenzimidazoline (BIH–R) and benzimidazolium (BI⁺–R) couples which were applied to the desulfonylative radical Truce–Smiles rearrangement. Expected rearrangement products formed in modest to good yields in these processes, in which added or in situ generated BIH–R serve as electron- and hydrogen-atom-donating reagents or photocatalysts. DFT calculations were carried out to gain the information about the radical intermediates involved in the rearrangement reaction.

Key words

benzimidazoline and benzimidazolium redox couple - single-electron transfer - photoreducing catalyst - radical Truce–Smiles rearrangement - desulfonylative aryl migration

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References

References and Notes

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Supplementary Material

Supporting Information