Title
The chemistry of zirconacycles and 2,6-diazasemibullvalenes [electronic resource] : synthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles / Shaoguang Zhang.
ISBN
9783662450215 electronic book
3662450216 electronic book
9783662450208
Published
Heidelberg : Springer, [2015]
Language
English
Description
1 online resource (xi, 173 pages) : illustrations (some color).
Item Number
10.1007/978-3-662-45021-5 doi
Call Number
QD411 .Z43 2015eb
Dewey Decimal Classification
547.05
Summary
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 ℓ́ℓchemical transformerℓ́ℓ upon treatment with various substrates via the ℓ́ℓcoordination-induced skeleton rearrangementℓ́ℓ 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 ℓ́ℓbowl-shapeℓ́ℓ or ℓ́ℓcage-shapeℓ́ℓ 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.
Note
"Doctoral thesis accepted by Peking University, Beijing, China."
Bibliography, etc. Note
Includes bibliographical references.
Access Note
Access limited to authorized users.
Source of Description
Online resource; title from PDF title page (SpringerLink, viewed December 19, 2014).
Series
Springer theses.
Available in Other Form
Print version: 9783662450208
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.
