Formation of silicon centered spirocyclic compounds: reaction of N-heterocyclic stable silylene with benzoylpyridine, diisopropyl azodicarboxylate, and 1,2-diphenylhydrazine |
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Authors: | Azhakar Ramachandran Sarish Sankaranarayana Pillai Tavcar Gasper Roesky Herbert W Hey Jakob Stalke Dietmar Koley Debasis |
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Institution: | Institut fu?r Anorganische Chemie, Universita?t Go?ttingen, Go?ttingen, Germany. |
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Abstract: | 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. |
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