| |
|
|
|
|
|
|
|
|
1. |
Record Nr. |
UNINA9910298612803321 |
|
|
Autore |
Zhang Shaoguang |
|
|
Titolo |
The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes : Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles / / by Shaoguang Zhang |
|
|
|
|
|
|
|
Pubbl/distr/stampa |
|
|
Berlin, Heidelberg : , : Springer Berlin Heidelberg : , : Imprint : Springer, , 2015 |
|
|
|
|
|
|
|
|
|
ISBN |
|
|
|
|
|
|
Edizione |
[1st ed. 2015.] |
|
|
|
|
|
Descrizione fisica |
|
1 online resource (182 p.) |
|
|
|
|
|
|
Collana |
|
Springer Theses, Recognizing Outstanding Ph.D. Research, , 2190-5053 |
|
|
|
|
|
|
|
|
Disciplina |
|
|
|
|
|
|
Soggetti |
|
Organometallic chemistry |
Chemistry, Physical and theoretical |
Crystallography |
Organometallic Chemistry |
Physical Chemistry |
Theoretical and Computational Chemistry |
Crystallography and Scattering Methods |
|
|
|
|
|
|
|
|
Lingua di pubblicazione |
|
|
|
|
|
|
Formato |
Materiale a stampa |
|
|
|
|
|
Livello bibliografico |
Monografia |
|
|
|
|
|
Note generali |
|
"Doctoral Thesis accepted by Peking University, Beijing, China." |
|
|
|
|
|
|
Nota di bibliografia |
|
Includes bibliographical references at the end of each chapters. |
|
|
|
|
|
|
Nota di contenuto |
|
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. |
|
|
|
|
|
|
|
|
Sommario/riassunto |
|
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. |
|
|
|
|
|
| |