TY - BOOK ID - 4868004 TI - The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes : Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles PY - 2015 SN - 9783662450215 3662450208 9783662450208 3662450216 PB - Berlin, Heidelberg : Springer Berlin Heidelberg : Imprint: Springer, DB - UniCat KW - Chemistry. KW - Organometallic Chemistry. KW - Physical Chemistry. KW - Theoretical and Computational Chemistry. KW - Crystallography. KW - Chemistry, Organic. KW - Chemistry, Physical organic. KW - Chimie KW - Chimie organique KW - Cristallographie KW - Metal complexes. KW - Organometallic chemistry -- Research. KW - Organometallic compounds. KW - Polymers. KW - Chemistry KW - Physical Sciences & Mathematics KW - Organic Chemistry KW - Metallo-organic compounds KW - Metalloids, Organic KW - Metalorganic compounds KW - Organometalloids KW - Organometallic chemistry. KW - Physical chemistry. KW - Chemistry, Physical and theoretical. KW - Organic compounds KW - Crystallography and Scattering Methods. KW - Leptology KW - Physical sciences KW - Mineralogy KW - Chemistry, Physical organic KW - Chemistry, Organic KW - Chemistry, Physical and theoretical KW - Organic chemistry KW - Organometallic chemistry . KW - Chemistry, Theoretical KW - Physical chemistry KW - Theoretical chemistry KW - Chemistry, Organometallic KW - Metallo-organic chemistry UR - https://www.unicat.be/uniCat?func=search&query=sysid:4868004 AB - 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. ER -