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The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes = 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
正題名/作者:	The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes/ by Shaoguang Zhang.
其他題名:	Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /
作者:	Zhang, Shaoguang.
面頁冊數:	XI, 173 p. 131 illus., 5 illus. in color.online resource. :
Contained By:	Springer Nature eBook
標題:	Organometallic chemistry . -
電子資源:	https://doi.org/10.1007/978-3-662-45021-5
ISBN:	9783662450215

The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes = Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /
Zhang, Shaoguang.

The Chemistry of Zirconacycles and 2,6-DiazasemibullvalenesSynthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /[electronic resource] :by Shaoguang Zhang. - 1st ed. 2015. - XI, 173 p. 131 illus., 5 illus. in color.online resource. - Springer Theses, Recognizing Outstanding Ph.D. Research,2190-5053. - Springer Theses, Recognizing Outstanding Ph.D. Research,.

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.

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.

ISBN: 9783662450215

Standard No.: 10.1007/978-3-662-45021-5doiSubjects--Topical Terms:

1254952
Organometallic chemistry .

LC Class. No.: QD410-412.5

Dewey Class. No.: 547.05

The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes = Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /
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