Reaction of 3-methylenebicyclo[3.3.1]nonan-7-one with amines

Conclusions 3-Methylenebicyclo[3.3.1]nonan-7-one forms addition products with piperidine and N,N-dimethylaniline in the presence of their hydrochlorides, but with piperidine in the presence of its hydrochloride it forms 1,3-dipiperidinoadamantane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1161–1163, May, 1986.     

Mechanism of transannular iodination of 3,7-dimethylenebicyclo[3.3.1]nonane derivatives

The kinetics of iodination of 3,7-dimethylenebicyclo[3.3.1]nonane derivatives containing alkyl substituents in one of the methylene groups were studied. The processes proceed selectively with the formation of 1-iodomethyl-3-iodoadamantanes, substituted at the 2-position, and characterized by a negative temperature dependence of the reaction rate (H=–(10–24) kJ/mole). The entropy contributions of the substituents at the double bonds to the reaction kinetics were determined; these contributions completely satisfy the Benson rules for synchronous transformations. A scheme of reaction mechanism was proposed, including the successive formation of diolefin complexes with iodine with a 11 and 12 compositions, a synchronous stage of ring closure with the formation of an ionic pair, and its recombination (the molecular-ionic mechanism).Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 743–747, November–December, 1986.     

Experimental and theoretical studies on the transannular cyclizations of 3,7-dimethylenebicyclo[3.3.1]nonane with polyfluoroalkyl radicals

Radical cyclizations of 3,7-dimethylenebicyclo[3.3.1]nonane with CF₃I, n-C₃F₇I, ICF₂COOEt and ICF₂PO(OEt)₂ selectively led to corresponding 3,7-noradamantanes, which were used for preparation of various polyfluoroalkyl substituted noradamantyl amines and carboxylates. DFT computations revealed that chemoselectivity of the radical cyclizations is realized due to the high electrophilicity of the CF₃ radical, as well as due to efficient trapping of intermediate noradamantylmethyl radicals by perfluoroiodoalkane.     

Cyclopalladate complex of 3-benzyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane

Russian Chemical Bulletin - A new (C,N,N)-pincer cyclopalladate unsymmetrical complex of 3-benzyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane (3-benzyl-7-methylbispidine) was synthesized and...     

New stereoselective intramolecular redox reaction in the system of 3,7-diazabicyclo[3.3.1]nonan-9-one

The ring opening in the 1-benzyl-5,7-dimethyl-6-oxo-1-azonia-3-azaadamantane chloride under the treatment with excess aqueous alkali led to a stereoselective formation of anti-1,5-dimethyl-7-benzyl-3-formyl-3,7-diazabicyclo[3.3.1]nonan-9-ol whose structure was established by means of X-ray diffraction analysis and NMR spectroscopy. A reaction mechanism was suggested involving an intramolecular redox hydride transfer.     

Synthesis of amphiphilic diacyl derivatives of 3,7-diazabicyclo[3.3.1]nonan-9-one

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Spatial Structure of Isomers of 3,7-Dialkoxyalkyl-3,7-diazabicyclo[3.3.1]nonan-9-ols

The spatial structure of 3,7-dialkoxyalkyl-3,7-diazabicyclo[3.3.1]nonan-9-ols has been investigated with the aid of ¹H and ¹³C NMR spectroscopy. It was shown that the secondary alcohols studied exist in solution predominantly in a chair-boat conformation which proved to be energetically more favorable than a chair-chair conformation due to the formation of an intramolecular hydrogen bond (IMHB) between the unshared pair of electrons on the nitrogen atom and the hydrogen atom of the hydroxyl group.     

Synthesis and Properties of 3-Thia-9-azabicyclo[3.3.1]nonan-7-one

N-Benzyl-3-thia-9-aza-bicyclo[3.3.1]nonan-7-one has been prepared from methyl 4-bromocrotonate by reaction sequence involving sodium sulfide, benzylamine, and Dieckmann condensation. Some spectral and chemical properties of this system are also reported.     

The gas-phase conformation of 3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonane

The gas-phase conformation of the title compound (1) is discussed in reference to its photoelectron spectrum. The experimental lone-pair/lone-pair splitting (0.51 eV), when compared with that of similar diamines and with the results of three sets of MO calculations (MINDO/3, MNDO and STO-3G), leads to the conclusion that 1 exists in the chair-chair conformation. A remarkable sensitivity of the calculations to slight changes in the geometry is noted, and it is suggested that calculations of this type must include geometry-optimization. The question of through-space vs through-bond inteaction of the nitrogen lone pairs was explored by performing MNDO calculations in which the N-N resonance integrals were set to zero. These calculations indicate that in the chair-chair conformation the N-N interaction is mainly through-space. The ¹³CNMR and Ni(acac)₂-induced ¹³C shifts of 1 are discussed.     

pH-Sensitive liposomes with embedded 3,7-diazabicyclo[3.3.1]nonane derivative

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