Overview
- Nominated by Peking University as an Excellent Doctoral Dissertation
- Describes the synthesis of synthetically useful N-heterocycles using Zr/Si-containing intermediate as a "chemical transformer", which are difficult to synthesize by other means
- Presents in detail the determination of X-ray crystal structure, the measurement of activation barrier of aza-Cope rearrangement, as well as the new reaction chemistry of 2,6-diazasemibullvalene (NSBV)
- Demonstrates for the first time the localized structure of NSBV as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium via theoretical analysis
- Research work was highlighted by J. Am. Chem. Soc. Spotlight
- Includes supplementary material: sn.pub/extras
Part of the book series: Springer Theses (Springer Theses)
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Table of contents (6 chapters)
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Front Matter
Keywords
About this book
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.
Authors and Affiliations
Bibliographic Information
Book Title: The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes
Book Subtitle: Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles
Authors: Shaoguang Zhang
Series Title: Springer Theses
DOI: https://doi.org/10.1007/978-3-662-45021-5
Publisher: Springer Berlin, Heidelberg
eBook Packages: Chemistry and Materials Science, Chemistry and Material Science (R0)
Copyright Information: Springer-Verlag Berlin Heidelberg 2015
Hardcover ISBN: 978-3-662-45020-8Published: 19 November 2014
Softcover ISBN: 978-3-662-51514-3Published: 23 August 2016
eBook ISBN: 978-3-662-45021-5Published: 05 November 2014
Series ISSN: 2190-5053
Series E-ISSN: 2190-5061
Edition Number: 1
Number of Pages: XI, 173
Number of Illustrations: 126 b/w illustrations, 5 illustrations in colour
Topics: Organometallic Chemistry, Physical Chemistry, Theoretical and Computational Chemistry, Crystallography and Scattering Methods