TY  - GEN
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 ℓ́ℓchemical transformerℓ́ℓ upon treatment with various substrates via the ℓ́ℓcoordination-induced skeleton rearrangementℓ́ℓ 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 ℓ́ℓbowl-shapeℓ́ℓ or ℓ́ℓcage-shapeℓ́ℓ 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.
AU  - Zhang, Shaoguang,
CN  - QD411
DO  - 10.1007/978-3-662-45021-5
DO  - doi
ID  - 724187
KW  - Organometallic compounds.
LK  - https://univsouthin.idm.oclc.org/login?url=http://link.springer.com/10.1007/978-3-662-45021-5
N1  - "Doctoral thesis accepted by Peking University, Beijing, China."
N2  - 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 ℓ́ℓchemical transformerℓ́ℓ upon treatment with various substrates via the ℓ́ℓcoordination-induced skeleton rearrangementℓ́ℓ 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 ℓ́ℓbowl-shapeℓ́ℓ or ℓ́ℓcage-shapeℓ́ℓ 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.
SN  - 9783662450215
SN  - 3662450216
T1  - The chemistry of zirconacycles and 2,6-diazasemibullvalenessynthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles /
TI  - The chemistry of zirconacycles and 2,6-diazasemibullvalenessynthesis, structures, reactions, and applications in the synthesis of novel N-heterocycles /
UR  - https://univsouthin.idm.oclc.org/login?url=http://link.springer.com/10.1007/978-3-662-45021-5
ER  -