The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes
Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles
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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.
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.
| Erscheinungsdatum | 29.08.2016 |
|---|---|
| Reihe/Serie | Springer Theses |
| Zusatzinfo | XI, 173 p. 131 illus., 5 illus. in color. |
| Verlagsort | Berlin |
| Sprache | englisch |
| Maße | 155 x 235 mm |
| Themenwelt | Naturwissenschaften ► Chemie ► Organische Chemie |
| Naturwissenschaften ► Chemie ► Physikalische Chemie | |
| Naturwissenschaften ► Physik / Astronomie ► Festkörperphysik | |
| Schlagworte | 2,6-diazasemibullvalene • Chemical Transformer • Chemistry and Materials Science • Condensed matter physics (liquid state and solid s • Cope Rearrangement • crystallography • Multi-component Cyclization • N-heterocycle • Organometallic Chemistry • Physical Chemistry • Poly-cyclic Skeleton • Quantum and theoretical chemistry • Reactive Intermediate • theoretical and computational chemistry • Zirconacycle • Zirconacyclobutene-silacyclobutene fused Compound |
| ISBN-13 | 9783662515143 / 9783662515143 |
| Zustand | Neuware |
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