Citation: Yaqi Deng, Jian Xue, Xiang Wu, Shunying Liu. Highly regioselective electrochemical oxidative 2,1-azolization of alkenes with azoles and nucleophiles[J]. Chinese Chemical Letters, ;2025, 36(9): 110822. doi: 10.1016/j.cclet.2025.110822 shu

Highly regioselective electrochemical oxidative 2,1-azolization of alkenes with azoles and nucleophiles

Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

syliu@sist.ecnu.edu.cn

Received Date: 18 July 2024
Revised Date: 27 December 2024
Accepted Date: 6 January 2025
Available Online: 7 January 2025

Figures(6)

The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.
- Alkenes,
- Difunctionalization,
- Hydroxyazolization,
- Electrochemical oxidative,
- Nitrogen-centered radicals
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