Erschienen: 23.08.2016 Abbildung von Zhang | The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes | Softcover reprint of the original 1st ed. 2015 | 2016 | Synthesis, Structures, Reactio...

Zhang

The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes

Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles

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Softcover reprint of the original 1st ed. 2015 2016. Buch. xi, 173 S. 126 s/w-Abbildungen, 5 Farbabbildungen, 10 s/w-Tabelle, Bibliographien. Softcover

Springer. ISBN 978-3-662-51514-3

Format (B x L): 15,5 x 23,5 cm

Gewicht: 297 g

In englischer Sprache

Das Werk ist Teil der Reihe: Springer Theses

Produktbeschreibung

In this thesis, the author introduces two strategies used to construct various types of N-heterocycles, based on the chemistry of zirconacycles and 2,6-diazasemibullvalenes. In the first part, the author presents the development of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. These reactions provide synthetically useful methodology for various N-heterocycles such as 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, which are all difficult to synthesize by other means. The isolation and characterization of the key three-fused-ring Zr/Si-containing intermediates are also described in detail. These results show that the zirconacyclobutene-silacyclobutene fused compound behaves as a “chemical transformer” upon treatment with various substrates via the “coordination-induced skeleton rearrangement” mechanism. In the second part, the author demonstrates the synthesis and isolation of a series of 2,6-diazasemibullvalenes (NSBVs) from the reaction of 1,4-dilithio-1,3-dienes and nitriles, highlighting the significant progress made for the first time in this work: (1) determination of X-ray crystal structure of a substituted 2,6-diazasemibullvalene; (2) measurement of the activation barrier of its rapid intramolecular aza-Cope rearrangement in solution; (3) exploration of several reaction types of NSBV with diverse ring-expansion products and “bowl-shape” or “cage-shape” N-containing polycyclic skeletons; (4) demonstration of the localized structure as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium using theoretical analysis. Based on well-founded results, this work sheds new light on this controversial topic.

Gesamtwerk

Die 8. Auflage ist wieder auf sechs Bände angelegt. Darin finden sich übersichtlich und in systematischer Gliederung Vertragsmuster aus der Feder erfahrener Experten. Jedem dieser Muster folgen Anmerkungen, mit denen der dem Vertragsentwurf zu Grunde liegende Sachverhalt und die Gründe für die Wahl des spezifischen Formulars erläutert werden.

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