(4+3) Cycloaddition Reactions of N‐Alkyl Oxidopyridinium Ions

N‐Methylation of methyl 5‐hydroxynicotinate followed by reaction with a diene in the presence of triethylamine afforded (4+3) cycloadducts in good to excellent yields. High regioselectivity was observed with 1‐substituted and 1,2‐disubstituted butadienes. Density functional theory calculations indic...

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Bibliographic Details
Published in:Angewandte Chemie 2017-11, Vol.129 (46), p.14874-14879
Main Authors: Fu, Chencheng, Lora, Nestor, Kirchhoefer, Patrick L., Lee, Dong Reyoul, Altenhofer, Erich, Barnes, Charles L., Hungerford, Natasha L., Krenske, Elizabeth H., Harmata, Michael
Format: Article
Language:English
Subjects:
(4+3)-Cycloaddition
Alkaloide
Alkaloids
Chemistry
Cycloaddition
Diene
Methylation
Pyridinium-Ionen
Regioselectivity
Triethylamine
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Summary:N‐Methylation of methyl 5‐hydroxynicotinate followed by reaction with a diene in the presence of triethylamine afforded (4+3) cycloadducts in good to excellent yields. High regioselectivity was observed with 1‐substituted and 1,2‐disubstituted butadienes. Density functional theory calculations indicate that the cycloaddition involves concerted addition of the diene onto the oxidopyridinium ion. The process provides rapid access to bicyclic nitrogenous structures resembling natural alkaloids. Größer als die Summe der Teile: N‐methyliertes Methyl‐5‐hydroxynicotinat reagiert durch (4+3)‐Cycloaddition mit Dienen in Gegenwart von Triethylamin zu bicyclischen stickstoffhaltigen Strukturen mit Ähnlichkeit zu natürlichen Alkaloiden (siehe Schema). Hohe Regioselektivitäten wurden mit 1‐substituierten und 1,2‐disubstituierten Butadienen beobachtet. Dichtefunktionalrechnungen belegen eine konzertierte Addition des Diens an das Oxidopyridinium‐Ion.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201708320