Syntheses of [alpha]-Alkylated [beta], [gamma]-Unsaturated [alpha]-Amino Acids

Various α-alkylated β, γ-unsaturated α-amino acids were synthesized by the deconjugative alkylation of methyl α-isocyanoalkylideneacetates followed by hydrolysis. In the mechanistic study, no marked differences in reactivity of the geometrical isomers of methyl 2-isocyano-3-phenyl-2-butenoate (E-and...

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Bibliographic Details
Published inChemical & pharmaceutical bulletin Vol. 30; no. 11; p. 4015
Main Authors NUNAMI, KENICHI, SUZUKI, MAMORU, YONEDA, NAOTO
Format Journal Article
LanguageEnglish
Published Tokyo Japan Science and Technology Agency 01.11.1982
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Summary:Various α-alkylated β, γ-unsaturated α-amino acids were synthesized by the deconjugative alkylation of methyl α-isocyanoalkylideneacetates followed by hydrolysis. In the mechanistic study, no marked differences in reactivity of the geometrical isomers of methyl 2-isocyano-3-phenyl-2-butenoate (E-and Z-11a) were observed. On the other hand, the double bound migration of unsymmetrical (R1≠R2) isocyano compounds (11c, d) proceeded regioselectively due both to the different acidities of the alkyl groups and to the stability of the carbanion formed on proton abstraction. Furthermore, direct synthesis of methyl α-isocyanocycloalkylideneacetates (4a, b, d) by the reaction of methyl isocyanoacetate with cyclic ketones was also investigated.
ISSN:0009-2363
1347-5223