A hydrogen-bonding-modulated molecular rotor: environmental effect in the conformational stability of peptidomimetic macrocyclic cyclophanes

The Journal of Organic Chemistry
Ignacio AlfonsoSantiago V Luis

Abstract

The conformational behavior of 16- to 18-membered ring peptidomimetic p-cyclophanes 1a,b-3a,b has been studied by NMR. The cycles bearing 16 and 17 atoms showed a dynamic process within the NMR time scale, produced by the rotation of the aromatic p-diphenylene moiety with respect to the macrocyclic main plane. The temperature dependence of 1H NMR spectra has been studied in order to get activation parameters of the energetic barrier for the process (VT-NMR and line shape analysis). The rate of the movement clearly depends on the macrocyclic ring size and the nature of the peptidomimetic side chain. Entropic and enthalpic contributions to the free energy of activation are discussed. The rotation of the aromatic ring is closely related to the intramolecular hydrogen bonding pattern, as suggested by temperature factors of NH chemical shifts (DeltadeltaNH/DeltaT) and molecular modeling. The interconnected roles of the solvation and the intramolecular H-bonds have been established by measurements (VT-NMR and DeltadeltaNH/DeltaT) in environments of different polarities and H-bonding abilities. We concluded that the conformational stability of the systems directly depends on the stability of the intramolecular H-bonding pattern. We fi...Continue Reading

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Citations

Aug 22, 2013·Accounts of Chemical Research·Santiago V Luis, I Alfonso
Nov 13, 2015·Chemical Communications : Chem Comm·Ignacio Alfonso
Nov 7, 2017·Chemical Communications : Chem Comm·Gregory T RushtonKen D Shimizu
Aug 15, 2006·Angewandte Chemie·Miriam BruSantiago V Luis
Dec 10, 2009·Chemistry : a European Journal·Ignacio AlfonsoSantiago V Luis
Sep 10, 2010·Chemistry : a European Journal·Wei-Ting SunJye-Shane Yang
Jan 21, 2012·Chemistry : a European Journal·Vicente Martí-CentellesSantiago V Luis
Apr 24, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Inés MartíSantiago V Luis
Aug 14, 2019·Chemical Communications : Chem Comm·Joan AtcherIvan Huc
Feb 9, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lingaraju GorlaSantiago V Luis
Aug 4, 2020·Chemistry : a European Journal·Pronay Kumar BiswasMichael Schmittel
Apr 12, 2008·Journal of the American Chemical Society·Ignacio AlfonsoJenifer Rubio
May 6, 2008·Organic Letters·Jye-Shane YangIto Chao
Oct 24, 2008·The Journal of Physical Chemistry. a·Giovanni F Caramori, Sérgio E Galembeck
Aug 5, 2010·Inorganic Chemistry·Salvador BlascoSantiago V Luis
Nov 15, 2011·The Journal of Organic Chemistry·Vicente Martí-CentellesRamón Vilar
Dec 9, 2010·Organic Letters·Brent E DialKen D Shimizu
Feb 11, 2012·Journal of the American Chemical Society·Brent E DialKen D Shimizu
Nov 4, 2006·The Journal of Organic Chemistry·V Balraju, Javed Iqbal

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