Browsing by Subject "Template synthesis"

Now showing 1 - 3 of 3
  • Thumbnail Image
    Publication
    Open Access
    Effects on Rotational Dynamics of Azo and Hydrazodicarboxamide-Based Rotaxanes
    (Multidisciplinary Digital Publishing Institute, 2017-06-28) Saura Sanmartín, Adrián; Martinez-Espin, Juan S.; Martinez-Cuezva, Alberto; Alajarín, Mateo; Berna, José; Berna, José; Química Orgánica
    The synthesis of novel hydrogen-bonded [2]rotaxanes having two pyridine rings in the macrocycle and azo- and hydrazodicarboxamide-based templates decorated with four cyclohexyl groups is described. The different affinity of the binding sites for the benzylic amide macrocycle and the formation of programmed non-covalent interactions between the interlocked components have an important effect on the dynamic behavior of these compounds. Having this in mind, the chemical interconversion between the azo and hydrazo forms of the [2]rotaxane was investigated to provide a chemically-driven interlocked system enable to switch its circumrotation rate as a function of the oxidation level of the binding site. Different structural modifications were carried out to further functionalize the nitrogen of the pyridine rings, including oxidation, alkylation or protonation reactions, affording interlocked azo-derivatives whose rotation dynamics were also analyzed.
  • Thumbnail Image
    Publication
    Open Access
    Enantioselective Formation of 2-Azetidinones by Ring-Assisted Cyclization of Interlocked N-(alpha-Methyl)benzyl Fumaramides
    (WILEY-VCH VERLAG GMBH, 2018-04-16) Martinez-Cuezva, Alberto; Bautista, Delia; Alajarín, Mateo; Berná Cánovas, José; Química Orgánica
    The synthesis of optically active interlocked and non-interlocked 2-azetidinones by intramolecular cyclization of N-(alpha-methyl)benzyl fumaramide [2]rotaxanes is described. Two different strategies of asymmetric induction were tested in which the chiral group was located either proximal or distal to the reacting center of the thread. During these experiments, an interesting equilibration process inside the macrocyclic void occurred, thus leading to the cyclization through the (alpha-methyl)benzyl carbon atom and giving rise to beta-lactams, with a quaternary carbon atom, in an enantio- and diastereocontrolled manner. This cyclization also proceeds in kinetically stable chiral pseudo[2]rotaxanes, thus allowing further de threading to provide enantioenriched 3,4-disubstituted trans-2-azetidinones. The stereochemical outcomes of the cyclization inside and outside the macrocycle demonstrated noticeable
  • Repository logo
    Publication
    Open Access
    FAIR data for compunds included in the article "Maximizing the [c2]daisy chain to lasso ratio through competitive self-templating clipping reactions"
    (Universidad de Murcia, 2021-11-30) Saura-Sanmartin, Adrian; Pastor Vivero, Aurelia; Martinez-Cuezva, Alberto; Berná Cánovas, José; Química orgánica