Springer Theses

The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes

Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles

Authors: Zhang, Shaoguang

  • 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
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  • ISBN 978-3-662-45021-5
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Hardcover $129.00
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  • ISBN 978-3-662-45020-8
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  • Usually dispatched within 3 to 5 business days.
Softcover $129.00
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  • ISBN 978-3-662-51514-3
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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.

Table of contents (6 chapters)

  • Introduction to Zirconacycle Chemistry

    Zhang, Shaoguang

    Pages 1-20

  • 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

    Zhang, Shaoguang

    Pages 21-61

  • Bulky Nitrile Coordination-Induced Skeleton Rearrangement of Zr-/Si-Containing Metallacycles and Selective Synthesis of 5-Azaindoles

    Zhang, Shaoguang

    Pages 63-90

  • Introduction to Semibullvalenes and Azasemibullvalenes

    Zhang, Shaoguang

    Pages 91-107

  • 2,6-Diazasemibullvalenes: Synthesis, Structural Characterization, and Theoretical Analysis

    Zhang, Shaoguang

    Pages 109-125

Buy this book

eBook $99.00
price for USA (gross)
  • ISBN 978-3-662-45021-5
  • Digitally watermarked, DRM-free
  • Included format: PDF, EPUB
  • ebooks can be used on all reading devices
  • Immediate eBook download after purchase
Hardcover $129.00
price for USA
  • ISBN 978-3-662-45020-8
  • Free shipping for individuals worldwide
  • Usually dispatched within 3 to 5 business days.
Softcover $129.00
price for USA
  • ISBN 978-3-662-51514-3
  • Free shipping for individuals worldwide
  • Usually dispatched within 3 to 5 business days.
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Bibliographic Information

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
Series Title
Springer Theses
Copyright
2015
Publisher
Springer-Verlag Berlin Heidelberg
Copyright Holder
Springer-Verlag Berlin Heidelberg
eBook ISBN
978-3-662-45021-5
DOI
10.1007/978-3-662-45021-5
Hardcover ISBN
978-3-662-45020-8
Softcover ISBN
978-3-662-51514-3
Series ISSN
2190-5053
Edition Number
1
Number of Pages
XI, 173
Number of Illustrations and Tables
126 b/w illustrations, 5 illustrations in colour
Topics