Electrolysis-Assisted Reduction of Dimethylformamide for Unactivated Alkene Functionalizations

TL;DR

This paper introduces a new method to use dimethylformamide as a reagent for chemical reactions involving alkenes.

Contribution

A novel electrolysis-assisted approach to generate a radical anion from dimethylformamide for alkene functionalization.

Findings

Electrolysis successfully generates a distonic radical anion from dimethylformamide.

The radical anion enables functionalization of unactivated alkenes into hydroformylated and hydroaminomethylated products.

Mechanistic studies confirm radical generation at the magnesium anode surface.

Abstract

N,N-Dimethylformamide is a widely used
solvent,
which can be employed as a reagent under certain conditions. Among
the different ionic and radical activation approaches, the direct
single-electron reduction of this amide appears elusive, owing to
its prohibitively low reductive potential. In this work, electrolysis-assisted
generation of the N,N-dimethylformamide distonic
radical anion is presented. Its synthetic applicability was established
by the functionalization of unactivated alkenes. The transformation
was validated across several mono- and disubstituted olefins, generating
the corresponding hydroformylated and hydroaminomethylated products.
Mechanistic experiments confirmed the generation of the distonic radical,
demonstrating that this intermediate was generated at the surface
of the magnesium anode. This work provides a new perspective on the
activation of this commonly used solvent, paving the way to other
radical transformations.

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