Formation of Silicon Centered Spirocyclic Compounds: Reaction of N-Heterocyclic Stable Silylene with Benzoylpyridine, Diisopropyl Azodicarboxylate, and 1,2-Diphenylhydrazine
| Autor: | Herbert W. Roesky, Sankaranarayana Pillai Sarish, Debasis Koley, Ramachandran Azhakar, Jakob Hey, Dietmar Stalke, Gašper Tavčar |
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| Rok vydání: | 2011 |
| Předmět: |
Models
Molecular Pyridines Diisopropyl azodicarboxylate Stereochemistry Hydrazone Crystallography X-Ray 010402 general chemistry Ring (chemistry) 01 natural sciences Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Heterocyclic Compounds silicon centered spirocyclic compounds Pyridine Organosilicon Compounds Spiro Compounds Physical and Theoretical Chemistry chemistry.chemical_classification Azo compound Molecular Structure 010405 organic chemistry Silylene Nuclear magnetic resonance spectroscopy Silanes Phenylhydrazines 0104 chemical sciences chemistry Carbamates Azo Compounds Derivative (chemistry) |
| Zdroj: | Inorganic Chemistry. 50:3028-3036 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic102566c |
| Popis: | Three silicon centered spirocyclic compounds 1-3, possessing silicon fused six- and five-membered rings have been prepared by the reaction of NHSi (L) [L = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}Si] with benzoylpyridine, diisopropyl azodicarboxylate, and 1,2-diphenylhydrazine, respectively, in a 1:1 ratio. The three spirocyclic compounds (1- 3) were obtained by three different pathways. The reaction of L with benzoylpyridine leads to the activation of the pyridine ring, and dearomatization occurred. Treatment of diisopropyl azodicarboxylate with L favors a [1 + 4]- rather than a [1 + 2]-cycloaddition product, and the azo compound was converted to hydrazone derivative. Finally the reaction of 1,2-diphenylhydrazine and L results in the elimination of hydrogen by activating one of the C-H bonds present in the phenyl ring. All three complexes 1- 3 were characterized by single crystal X-ray structural analysis, NMR spectroscopy, EI-MS spectrometry, and elemental analysis. In addition the optimized structures of probable products and possible intermediates were investigated using density functional theory (DFT) calculations. peerReviewed |
| Databáze: | OpenAIRE |
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