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Synthesis and reactivity of beta-bromo-beta-substituted dehydroalanines

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Resumo:The methyl ester of N-tert-butoxycarbonyl-(Z)-beta-bromo-beta-(1,2,4-triazol-1-yl)dehydroalanine was prepared by treatment of the methyl ester of N-tert-butoxycarbonyl-(E)-beta-(1,2,4-triazol-1-yl)dehydroalanine with N-bromosuccinimide (NBS), followed by Et3N. The reactivities of this compound and of our previously synthesized methyl ester of N-tert-butoxycarbonyl-beta,beta-dibromodehydroalanine towards several nucleophiles were studied, and it was found that these compounds react with oxygen nucleophiles to give the corresponding alpha-alkoxy-beta,beta-disubstituted alanines. Addition to the a-carbon atom also occurred when the beta,beta-dibromodehydroalanine derivative was treated with primary amines, giving alpha-amino-beta,beta-dibromoalanines. Treatment of the beta-bromo-beta-(1,2,4-triazol-1-yl)dehydroalanine derivative with amines gave alpha-(alkylamino)-beta-(alkylimino)alanines in high yields. These iminoalanines afforded alpha-aminoglycines when treated with silica in dichloromethane. (c) Wiley-VCH Verlag GmbH & Co.
Autores principais:Ferreira, Paula M. T.
Outros Autores:Monteiro, Luís S.
Assunto:Nonproteinogenic amino acids Alanine derivatives Glycine derivatives
Ano:2006
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso aberto
Instituição associada:Universidade do Minho
Idioma:inglês
Origem:RepositóriUM - Universidade do Minho
Descrição
Resumo:The methyl ester of N-tert-butoxycarbonyl-(Z)-beta-bromo-beta-(1,2,4-triazol-1-yl)dehydroalanine was prepared by treatment of the methyl ester of N-tert-butoxycarbonyl-(E)-beta-(1,2,4-triazol-1-yl)dehydroalanine with N-bromosuccinimide (NBS), followed by Et3N. The reactivities of this compound and of our previously synthesized methyl ester of N-tert-butoxycarbonyl-beta,beta-dibromodehydroalanine towards several nucleophiles were studied, and it was found that these compounds react with oxygen nucleophiles to give the corresponding alpha-alkoxy-beta,beta-disubstituted alanines. Addition to the a-carbon atom also occurred when the beta,beta-dibromodehydroalanine derivative was treated with primary amines, giving alpha-amino-beta,beta-dibromoalanines. Treatment of the beta-bromo-beta-(1,2,4-triazol-1-yl)dehydroalanine derivative with amines gave alpha-(alkylamino)-beta-(alkylimino)alanines in high yields. These iminoalanines afforded alpha-aminoglycines when treated with silica in dichloromethane. (c) Wiley-VCH Verlag GmbH & Co.