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

Abstract

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.