Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids

The electrooxidative allylation of a carbamate was successfully demonstrated using 3-propylsulfonic acid-functionalized silica gel (Si-SCX-2). It was shown that the electrochemical oxidation of the carbamate as a first step yields the corresponding N-acyliminium ion equivalent at room temperature, a...

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Main Authors: Haruka HOMMA, Natsumi HONJO, Akihiro TAKABAYASHI, Toshiki TAJIMA
Format: Article
Language:English
Published: The Electrochemical Society of Japan 2025-06-01
Series:Electrochemistry
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Online Access:https://www.jstage.jst.go.jp/article/electrochemistry/93/6/93_25-00070/_html/-char/en
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author Haruka HOMMA
Natsumi HONJO
Akihiro TAKABAYASHI
Toshiki TAJIMA
author_facet Haruka HOMMA
Natsumi HONJO
Akihiro TAKABAYASHI
Toshiki TAJIMA
author_sort Haruka HOMMA
collection DOAJ
description The electrooxidative allylation of a carbamate was successfully demonstrated using 3-propylsulfonic acid-functionalized silica gel (Si-SCX-2). It was shown that the electrochemical oxidation of the carbamate as a first step yields the corresponding N-acyliminium ion equivalent at room temperature, and the reaction of the N-acyliminium ion equivalent with allyltrimethylsilane as a next step leads to allylation without the use of Lewis acids. It was also found that the HBF4 generated by the cation exchange reaction between the Si-SCX-2 and the supporting electrolyte plays an important role in this reaction system.
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id doaj-art-b734124fae884ba8acf8486cb2a4e110
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language English
publishDate 2025-06-01
publisher The Electrochemical Society of Japan
record_format Article
series Electrochemistry
spelling doaj-art-b734124fae884ba8acf8486cb2a4e1102025-08-20T02:10:25ZengThe Electrochemical Society of JapanElectrochemistry2186-24512025-06-0193606700306700310.5796/electrochemistry.25-00070electrochemistryMechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported AcidsHaruka HOMMA0https://orcid.org/0009-0005-0854-5261Natsumi HONJO1Akihiro TAKABAYASHI2Toshiki TAJIMA3https://orcid.org/0009-0000-8933-1225Graduate School of Engineering and Science, Shibaura Institute of TechnologyGraduate School of Engineering and Science, Shibaura Institute of TechnologyGraduate School of Engineering and Science, Shibaura Institute of TechnologyGraduate School of Engineering and Science, Shibaura Institute of TechnologyThe electrooxidative allylation of a carbamate was successfully demonstrated using 3-propylsulfonic acid-functionalized silica gel (Si-SCX-2). It was shown that the electrochemical oxidation of the carbamate as a first step yields the corresponding N-acyliminium ion equivalent at room temperature, and the reaction of the N-acyliminium ion equivalent with allyltrimethylsilane as a next step leads to allylation without the use of Lewis acids. It was also found that the HBF4 generated by the cation exchange reaction between the Si-SCX-2 and the supporting electrolyte plays an important role in this reaction system.https://www.jstage.jst.go.jp/article/electrochemistry/93/6/93_25-00070/_html/-char/enelectrooxidative allylationn-acyliminium ionsolid-supported acidcation exchange reaction
spellingShingle Haruka HOMMA
Natsumi HONJO
Akihiro TAKABAYASHI
Toshiki TAJIMA
Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
Electrochemistry
electrooxidative allylation
n-acyliminium ion
solid-supported acid
cation exchange reaction
title Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
title_full Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
title_fullStr Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
title_full_unstemmed Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
title_short Mechanistic Insights into Electrooxidative Allylation of a Carbamate in the Presence of Solid-Supported Acids
title_sort mechanistic insights into electrooxidative allylation of a carbamate in the presence of solid supported acids
topic electrooxidative allylation
n-acyliminium ion
solid-supported acid
cation exchange reaction
url https://www.jstage.jst.go.jp/article/electrochemistry/93/6/93_25-00070/_html/-char/en
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AT natsumihonjo mechanisticinsightsintoelectrooxidativeallylationofacarbamateinthepresenceofsolidsupportedacids
AT akihirotakabayashi mechanisticinsightsintoelectrooxidativeallylationofacarbamateinthepresenceofsolidsupportedacids
AT toshikitajima mechanisticinsightsintoelectrooxidativeallylationofacarbamateinthepresenceofsolidsupportedacids