Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates

The N,O-acetal derived from diethyl mesoxalate (DEMO) undergoes elimination of acetic acid upon treatment with a base, leading to the formation of N-acylimine in situ. Lithium acetylide readily attacks the imino group to afford N,1,1-tricarbonylated propargylamines. When the resulting propargylamine...

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Main Authors: Kento Iwai, Akari Hikasa, Kotaro Yoshioka, Shinki Tani, Kazuto Umezu, Nagatoshi Nishiwaki
Format: Article
Language:English
Published: Beilstein-Institut 2024-11-01
Series:Beilstein Journal of Organic Chemistry
Subjects:
Online Access:https://doi.org/10.3762/bjoc.20.238
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author Kento Iwai
Akari Hikasa
Kotaro Yoshioka
Shinki Tani
Kazuto Umezu
Nagatoshi Nishiwaki
author_facet Kento Iwai
Akari Hikasa
Kotaro Yoshioka
Shinki Tani
Kazuto Umezu
Nagatoshi Nishiwaki
author_sort Kento Iwai
collection DOAJ
description The N,O-acetal derived from diethyl mesoxalate (DEMO) undergoes elimination of acetic acid upon treatment with a base, leading to the formation of N-acylimine in situ. Lithium acetylide readily attacks the imino group to afford N,1,1-tricarbonylated propargylamines. When the resulting propargylamine reacts with butyllithium, ring closure occurs between the ethynyl and carbamoyl groups, yielding 2,5-disubstituted oxazole-4-carboxylates. This cyclization also occurs when the propargylamine is heated with ammonium acetate, resulting in double activation.
format Article
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institution Kabale University
issn 1860-5397
language English
publishDate 2024-11-01
publisher Beilstein-Institut
record_format Article
series Beilstein Journal of Organic Chemistry
spelling doaj-art-bb5f11a54a764fffb90fe1c0a1ec65f32024-12-02T08:46:11ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972024-11-012012827283310.3762/bjoc.20.2381860-5397-20-238Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylatesKento Iwai0Akari Hikasa1Kotaro Yoshioka2Shinki Tani3Kazuto Umezu4Nagatoshi Nishiwaki5School of Engineering Science, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan School of Engineering Science, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan Kumiai Chemical Industry Co. Ltd., Nakanogo, Fuji, Shizuoka 421-3306, Japan and 5K • I Chemical Industry Co. Ltd., Shinoshinden, Iwata, Shizuoka 437-1213, Japan Kumiai Chemical Industry Co. Ltd., Nakanogo, Fuji, Shizuoka 421-3306, Japan and 5K • I Chemical Industry Co. Ltd., Shinoshinden, Iwata, Shizuoka 437-1213, Japan Kumiai Chemical Industry Co. Ltd., Nakanogo, Fuji, Shizuoka 421-3306, Japan and 5K • I Chemical Industry Co. Ltd., Shinoshinden, Iwata, Shizuoka 437-1213, Japan School of Engineering Science, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan The N,O-acetal derived from diethyl mesoxalate (DEMO) undergoes elimination of acetic acid upon treatment with a base, leading to the formation of N-acylimine in situ. Lithium acetylide readily attacks the imino group to afford N,1,1-tricarbonylated propargylamines. When the resulting propargylamine reacts with butyllithium, ring closure occurs between the ethynyl and carbamoyl groups, yielding 2,5-disubstituted oxazole-4-carboxylates. This cyclization also occurs when the propargylamine is heated with ammonium acetate, resulting in double activation.https://doi.org/10.3762/bjoc.20.238acid amidediethyl mesoxalaten-acylamineoxazolepropargylamine
spellingShingle Kento Iwai
Akari Hikasa
Kotaro Yoshioka
Shinki Tani
Kazuto Umezu
Nagatoshi Nishiwaki
Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
Beilstein Journal of Organic Chemistry
acid amide
diethyl mesoxalate
n-acylamine
oxazole
propargylamine
title Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
title_full Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
title_fullStr Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
title_full_unstemmed Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
title_short Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates
title_sort synthesis of tricarbonylated propargylamine and conversion to 2 5 disubstituted oxazole 4 carboxylates
topic acid amide
diethyl mesoxalate
n-acylamine
oxazole
propargylamine
url https://doi.org/10.3762/bjoc.20.238
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