A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)

Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of t...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 59; no. 25; pp. 7635 - 7642
Main Authors Nunami, Ken-ichi, Yamada, Masaki, Fukui, Toshio, Matsumoto, Kazuo
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 01.12.1994
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ORGANIC-SYNTHESIS
SUBSTITUTION
AMINO-ACIDS
AGENTS
IMIDAZOLES
DEHYDROAMINO ACID-DERIVATIVES
ALPHA-METALATED ISOCYANIDES
STEREOSELECTIVE SYNTHESIS
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Summary:Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.
Bibliography:istex:DFDCB2C1C3980923C672BD8C2345A71445C230FE
ark:/67375/TPS-JCWK89XW-8
ISSN:0022-3263
1520-6904
DOI:10.1021/jo00104a018