ChemInform Abstract: An Example of a Facile Oxidative Dehydrogenation of Derivatives of 3‐Azabicyclo[3.3.1]nonane.

Omarov, T. T.; Amanzholov, I. A.; Sultanbaeva, B. M.; Kolesnikova, S. V.; Palyulin, V. A.; Зефиров, Н. С.

doi:10.1002/chin.198608079

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“…Crystals of 1 , 3 , 5 , 6 , and 7 suitable for XRD were obtained. The crystal structures of 3 and 5 have been previously reported [ 47 , 61 – 63 ]. The crystal structures of 1 , 6 , and 7 are reported for the first time.…”

Section: Resultsmentioning

confidence: 99%

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Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

Garcías-Morales¹,

Ortegón-Reyna²,

Ariza‐Castolo³

2015

Beilstein J. Org. Chem.

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SummaryThis paper reports the synthesis of a series of piperidones 1–8 by the Mannich reaction and analysis of their structures and conformations in solution by NMR and mass spectrometry. The six-membered rings in 2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-ones, compounds 1 and 2, adopt a chair–boat conformation, while those in 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ones, compounds 3–8, adopt a chair–chair conformation because of stereoelectronic effects. These stereoelectronic effects were analyzed by the 1 J C–H coupling constants, which were measured in the 13C satellites of the 1H NMR spectra obtained with the hetero-dqf pulse sequence. In the solid state, these stereoelectronic effects were investigated by measurement of X-ray diffraction data, the molecular geometry (torsional bond angles and bond distances), and inter- and intramolecular interactions, and by natural bond orbital analysis, which was performed using density functional theory at the ωB97XD/6311++G(d,p) level. We found that one of the main factors influencing the conformational stability of 3–8 is the interaction between the lone-pair electrons of nitrogen and the antibonding sigma orbital of C(7)–Heq (nN→σ*C–H(7)eq), a type of hyperconjugative interaction.

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Section: Resultsmentioning

confidence: 99%

“…This geometry allowed a C–H∙∙∙π intramolecular interaction between the aromatic rings. There are also C–H∙∙∙π intermolecular interactions [ 61 – 63 ]. Two intermolecular hydrogen bonds are observed for N(3)–H(3)∙∙∙O(1) ( Fig.…”

Section: Resultsmentioning

confidence: 99%