The chemistry of zirconacycles and 2...
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  • The chemistry of zirconacycles and 2,6-diazasemibullvalenes[electronic resource] :synthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles /
  • 紀錄類型: 書目-語言資料,印刷品 : Monograph/item
    杜威分類號: 547.05
    書名/作者: The chemistry of zirconacycles and 2,6-diazasemibullvalenes : synthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles // by Shaoguang Zhang.
    作者: Zhang, Shaoguang.
    出版者: Berlin, Heidelberg : : Springer Berlin Heidelberg :, 2015.
    面頁冊數: xi, 173 p. : : ill. (some col.), digital ;; 24 cm.
    Contained By: Springer eBooks
    標題: Organometallic compounds.
    標題: Chemistry.
    標題: Organometallic Chemistry.
    標題: Physical Chemistry.
    標題: Theoretical and Computational Chemistry.
    標題: Crystallography.
    ISBN: 9783662450215 (electronic bk.)
    ISBN: 9783662450208 (paper)
    內容註: Introduction to Zirconacycle Chemistry -- Zirconocene-Mediated Cyclization of Bis(alkynyl)silanes and Nitriles: Synthesis of N-Heterocycles and Isolation, Characterization and Synthetic Application of Zr/Si-containing Reactive Intermediates -- Bulky-Nitrile Coordination Induced Skeleton Rearrangement of Zr/Si-containing Metallacycles and Selective Synthesis of 5-Azaindoles -- Introduction to Semibullvalenes and Azasemibullvalenes -- 2,6-Diazasemibullvalenes: Synthesis, Structure, Theoretical Analysis and Computational Chemistry -- 2,6-Diazasemibullvalenes: Reaction Chemistry and Synthetic Application.
    摘要、提要註: 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.
    電子資源: http://dx.doi.org/10.1007/978-3-662-45021-5
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