05261nam 22007095 450 991029861280332120200701231436.03-662-45021-610.1007/978-3-662-45021-5(CKB)3710000000277564(EBL)1968604(SSID)ssj0001386394(PQKBManifestationID)11896947(PQKBTitleCode)TC0001386394(PQKBWorkID)11374071(PQKB)10016641(DE-He213)978-3-662-45021-5(MiAaPQ)EBC1968604(PPN)183098064(EXLCZ)99371000000027756420141105d2015 u| 0engur|n|---|||||txtccrThe Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles /by Shaoguang Zhang1st ed. 2015.Berlin, Heidelberg :Springer Berlin Heidelberg :Imprint: Springer,2015.1 online resource (182 p.)Springer Theses, Recognizing Outstanding Ph.D. Research,2190-5053"Doctoral Thesis accepted by Peking University, Beijing, China."3-662-45020-8 Includes bibliographical references at the end of each chapters.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.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.Springer Theses, Recognizing Outstanding Ph.D. Research,2190-5053Organometallic chemistryChemistry, Physical and theoreticalChemistry, Physical and theoreticalCrystallographyOrganometallic Chemistryhttps://scigraph.springernature.com/ontologies/product-market-codes/C19020Physical Chemistryhttps://scigraph.springernature.com/ontologies/product-market-codes/C21001Theoretical and Computational Chemistryhttps://scigraph.springernature.com/ontologies/product-market-codes/C25007Crystallography and Scattering Methodshttps://scigraph.springernature.com/ontologies/product-market-codes/P25056Organometallic chemistry.Chemistry, Physical and theoretical.Chemistry, Physical and theoretical.Crystallography.Organometallic Chemistry.Physical Chemistry.Theoretical and Computational Chemistry.Crystallography and Scattering Methods.547.05Zhang Shaoguangauthttp://id.loc.gov/vocabulary/relators/aut868709MiAaPQMiAaPQMiAaPQBOOK9910298612803321The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes1939231UNINA