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. 2025 May 15;1(8):1515-1522.
doi: 10.1021/acselectrochem.5c00111. eCollection 2025 Aug 7.

Electrochemical Ammoxidation of Unprotected Glycosides

Imke M A Bartels  1 , Md Asmaul Hoque  2 , J Prathap Kaniraj  1 , Mathew R Johnson  2 , Sebastian B Beil  1   3 , Shannon S Stahl  2 , Martin D Witte  1 , Adriaan J Minnaard  1
Affiliations

Electrochemical Ammoxidation of Unprotected Glycosides

Imke M A Bartels et al. ACS Electrochem. .

Abstract

Cyano-sugars are useful carbohydrate building blocks. Here, we report an electrocatalytic method to oxidize the primary alcohols of unprotected glycosides to the corresponding nitrile using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) as a mediator and ammonium tetrafluoroborate as the ammonia source. Monosaccharides and disaccharides undergo successful reactions in an acetonitrile/pyridine solvent mixture at room temperature under constant current electrolysis.

Keywords: Electrocatalytic oxidation; TEMPO; ammoxidation; carbohydrates; nitriles.

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Figures

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Context and strategy for the ammoxidation of carbohydrates.
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A) Electrochemical oxidation of methyl-2,3-di-O-benzyl-α-d-glucopyranoside 1 and methyl-α-d-glucopyranoside 3 using an IKA Electrasyn 2.0. B) Potential reaction pathways.
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A) TEMPO-catalyzed electrochemical oxidation of methyl-α-d-glucopyranoside. B) CVs (100 mV/s) in MeCN:pyridine 9:1 and NH4BF4 (0.3 M) of TEMPO (2 mM) (red trace); TEMPO (2 mM) and methyl-α-d-glucopyranoside (100 mM) (blue trace). All potentials are reported relative to those of Fc+/Fc.
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Electrochemical ammoxidation. Top graph: the constant current electrolysis trace. Bottom graph: the qNMR yield over time.
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Gram-scale electrochemical ammoxidation in a multi-electrode batch electrolysis reactor.
See this image and copyright information in PMC

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