By Shaoguang Zhang

In this thesis, the writer introduces options used to build quite a few varieties of N-heterocycles, in response to the chemistry of zirconacycles and 2,6-diazasemibullvalenes. within the first half, the writer provides the improvement of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. those reactions offer synthetically necessary technique for numerous N-heterocycles similar to 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, that are all tough to synthesize by means of different capability. The isolation and characterization of the most important three-fused-ring Zr/Si-containing intermediates also are defined intimately. those effects convey that the zirconacyclobutene-silacyclobutene fused compound behaves as a “chemical transformer” upon therapy with quite a few substrates through the “coordination-induced skeleton rearrangement” mechanism. within the moment half, the writer demonstrates the synthesis and isolation of a chain of 2,6-diazasemibullvalenes (NSBVs) from the response of 1,4-dilithio-1,3-dienes and nitriles, highlighting the numerous development made for the 1st time during this paintings: (1) selection of X-ray crystal constitution of a substituted 2,6-diazasemibullvalene; (2) size of the activation barrier of its speedy intramolecular aza-Cope rearrangement in resolution; (3) exploration of numerous response forms of NSBV with assorted ring-expansion items and “bowl-shape” or “cage-shape” N-containing polycyclic skeletons; (4) demonstration of the localized constitution because the foremost shape and the homoaromatic delocalized constitution as a minor part within the equilibrium utilizing theoretical research. in accordance with well-founded effects, this paintings sheds new gentle in this arguable topic.

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Extra resources for The Chemistry of Zirconacycles and 2,6-Diazasemibullvalenes: Synthesis, Structures, Reactions, and Applications in the Synthesis of Novel N-Heterocycles

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79 ppm. Dihydropyrrolo[3,2-c]azepine derivatives 2-18b and 2-19b could also be obtained. The hydrolysis mechanism from the bis(iminoacyl)–Zr intermediates to dihydropyrrolo[3,2-c]azepine derivatives 2-18 and 2-19 is not clear yet [37–39]. 5 One-Pot Synthesis of Pyrrolo[3,2-d]pyridazines and Pyrrole-2,3-Diones via Zirconocene-Mediated Four-Component Coupling of Bis(alkynyl)silane, Nitriles, and Azide Pyrrolo[3,2-d]pyridazines are a class of interesting and useful N-heterocycles [40–42]. However, synthetic methods for such heterocyclic compounds have been very much limited such as condensation of pyrrole-2,3-diones with hydrazine.

04. 0281. 2-1d: White solid, isolated yield 48 % (358 mg). 84. 0597. 75. 60. 2-1e: White solid, isolated yield 42 % (365 mg). 46 (s, 1H). 84. 9146. 22. 00. 2-1f: White solid, isolated yield 32 % (230 mg). 80. 2166. 87. 67. 2-1g: White solid, isolated yield 45 % (270 mg). 01. 2768. 5 mL). 025 mmol) was added, and then, the reaction mixture was refluxed for 16 h. The mixture was extracted with dichloromethane and washed with brine (100 mL × 3). The organic extracts were dried with anhydrous MgSO4.

10b). 10b), showing that the steric hinderance of isocyanides strongly affects the insertion reaction. 10c). 5 eq. 10 Formation of iminoacyl–Zr complexes by insertion of isocyanides into Zr–C(sp3) bond 32 2 Zirconocene-Mediated Cyclization of Bis(alkynyl)silanes and Nitriles … double insertion of isocyanides into Zr–C bonds is rare, and this work represents an efficient preparation of bis(iminoacyl)–Zr complexes [24–27]. These η2-iminoacyl–Zr complexes 2-14–2-16 were all characterized by 1H NMR and 13C NMR spectra.

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