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

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

Publication History

Received: 30 May 2023

Accepted after revision: 14 August 2023

Accepted Manuscript online:
14 August 2023

Article published online:
19 September 2023

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