Electrochemical N-Propargylation of N-Heterocycles via Decarboxylation of Allenoic Acids
Abstract
Broadly applicable and selective C–N bond formation remains a cornerstone challenge in organic synthesis. Although electrochemical methods have recently emerged as an efficient way for achieving decarboxylative C–N coupling, transforming allenoic acids into N-functionalized products remains elusive. Herein, we report the development of an electrochemical strategy for the decarboxylative N-propargylation of N-heterocycles using readily available 2,3-allenoic acids. By correlating the oxidation potentials of allenoic acids and nucleophilic coupling partners, we derived predictive criteria for anticipating reaction efficiency across a broad substrate scope. Mechanistic studies (cyclic voltammetry, in situ infrared (IR) kinetics, and density functional theory (DFT) calculations) support a two-step sequence involving oxidative decarboxylation to an allenyl radical rapidly oxidized to a highly electrophilic allenyl/propargyl cation and regioselective heterocycle attack yielding N-propargylated products. This work showcases a straightforward method for accessing reactive allenyl cation intermediates and expands the toolkit for sustainable electrosynthetic C–N bond formation.
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BibTeX
@article{abdoun2026electrochemical,
title = {{Electrochemical N-Propargylation of N-Heterocycles via Decarboxylation of Allenoic Acids}},
author = {Sarah Abdoun and Christophe Bour and Robert Mayer and Marie Vayer},
journal = {ACS Organic \& Inorganic Au},
year = {2026},
month = oct,
doi = {10.1021/acsorginorgau.5c00117},
url = {https://hal.science/hal-05771765v1},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Electrochemical N-Propargylation of N-Heterocycles via Decarboxylation of Allenoic Acids
AU - Sarah Abdoun
AU - Christophe Bour
AU - Robert Mayer
AU - Marie Vayer
PY - 2026
DA - 2026/10/06
JO - ACS Organic & Inorganic Au
DO - 10.1021/acsorginorgau.5c00117
UR - https://hal.science/hal-05771765v1
AB - Broadly applicable and selective C–N bond formation remains a cornerstone challenge in organic synthesis. Although electrochemical methods have recently emerged as an efficient way for achieving decarboxylative C–N coupling, transforming allenoic acids into N-functionalized products remains elusive. Herein, we report the development of an electrochemical strategy for the decarboxylative N-propargylation of N-heterocycles using readily available 2,3-allenoic acids. By correlating the oxidation potentials of allenoic acids and nucleophilic coupling partners, we derived predictive criteria for anticipating reaction efficiency across a broad substrate scope. Mechanistic studies (cyclic voltammetry, in situ infrared (IR) kinetics, and density functional theory (DFT) calculations) support a two-step sequence involving oxidative decarboxylation to an allenyl radical rapidly oxidized to a highly electrophilic allenyl/propargyl cation and regioselective heterocycle attack yielding N-propargylated products. This work showcases a straightforward method for accessing reactive allenyl cation intermediates and expands the toolkit for sustainable electrosynthetic C–N bond formation.
SN - 2694-247X
ER -