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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 /

纪录类型:	书目-语言数据,印刷品 : Monograph/item
[NT 15000414] null:	547.05
[NT 47271] Title/Author:	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.
面页册数:	xi, 173 p. : : ill. (some col.), digital ;; 24 cm.
Contained By:	Springer eBooks
标题:	Organometallic compounds.
标题:	Chemistry.
标题:	Organometallic Chemistry.
标题:	Physical Chemistry.
标题:	Theoretical and Computational Chemistry.
标题:	Crystallography.
ISBN:	9783662450215 (electronic bk.)
ISBN:	9783662450208 (paper)
[NT 15000228] null:	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.
[NT 15000229] null:	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.
电子资源:	http://dx.doi.org/10.1007/978-3-662-45021-5

The chemistry of zirconacycles and 2,6-diazasemibullvalenes[electronic resource] :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. - Berlin, Heidelberg :Springer Berlin Heidelberg :2015. - xi, 173 p. :ill. (some col.), digital ;24 cm. - Springer theses,2190-5053. - Springer theses..

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 (electronic bk.)

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

470495
Organometallic compounds.

LC Class. No.: QD411 / .Z43 2015

Dewey Class. No.: 547.05

The chemistry of zirconacycles and 2,6-diazasemibullvalenes[electronic resource] :synthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles /
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