Ring Closure Reactions of 2,6-Diazaheptatrienyl Metal Compounds: Synthesis of 3-Aminoindole Derivatives and 14-Membered Macrocyclic Dimers
2,6-Diazaheptatrienyl metal compounds 6 – K + are easily accessible from the corresponding diimines 6 by deprotonation using KO-t-Bu as base. According to quantum chemical calculations, they are, in comparison to other isomeric species with nitrogen atoms in other positions, highly reactive intermed...
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Veröffentlicht in: | Journal of organic chemistry 2011-11, Vol.76 (21), p.8794-8806 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | 2,6-Diazaheptatrienyl metal compounds 6 – K + are easily accessible from the corresponding diimines 6 by deprotonation using KO-t-Bu as base. According to quantum chemical calculations, they are, in comparison to other isomeric species with nitrogen atoms in other positions, highly reactive intermediates, which undergo in dilute solution at 50 °C ring closure reactions to form 3-aminoindole derivatives 8/10. In contrast, in more concentrated solution at room temperature, the formation of 14-membered macrocyclces 13 as a result of formal dimerization is observed. The 3-aminoindole derivatives obtained in this work possess rare substitution patterns, and the macrocyclic compounds are essentially unknown. Two-fold vinylogous derivatives 7 give rise to tricyclic systems with δ-carboline backbone 12. The experimental results are interpreted using high-level DFT calculations with regard to the possible reaction mechanism and the nature of the transition state of the five-membered ring formation. The molecular structures in the solid state of all types of compounds were elucidated by X-ray diffraction. |
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ISSN: | 0022-3263 1520-6904 |
DOI: | 10.1021/jo201521v |