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Chemistry - Organic Chemistry | The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes - Synthesis, Structures, Reactions,

The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes

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

Series: Springer Theses

Zhang, Shaoguang

2015, XI, 173 p. 131 illus., 5 illus. in color.

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  • 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

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.

Content Level » Research

Keywords » 2,6-diazasemibullvalene - Chemical Transformer - Cope Rearrangement - Multi-component Cyclization - N-heterocycle - Poly-cyclic Skeleton - Reactive Intermediate - Zirconacycle - Zirconacyclobutene-silacyclobutene fused Compound

Related subjects » Materials - Organic Chemistry - Physical Chemistry - Theoretical and Computational Chemistry

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