Asensio, Juan Luis

Bastida, Agatha

Corzana, Francisco

Gómez, Ana M.

Jiménez-Barbero, Jesús

Jiménez-Moreno, Ester

Jiménez-Oses, Gonzalo

Montalvillo-Jiménez, Laura

Repositorio de Universidad de La Rioja

1SCIENTIFIC PROGRAM& ABSTRACT BOOK723A DYNAMIC COMBINATORIAL CHEMISTRY APPROACH TO QUANTIFY THE CONTRIBUTION OF ELECTROSTATICS TO THE STABILITY OF CH/π BONDS IN WATERLaura Montalvillo-Jiménez1Departamento de Química Bio-orgánica, Instituto de Química Orgánica General (CSIC). Madrid. Spain.                                                                                                       2Departamento de Química, Universidad de la Rioja. Logroño (La Rioja). Spain.                                                                                                                      3CICbioGUNE, Parque Tecnológico de Bizkaia. Derio- Bizkaia. Spain.                        , 1 Ester Jiménez-Moreno,1 Ana M. Gómez,1 Agatha Bastida,1Francisco Corzana,2 Gonzalo Jiménez-Oses,2 Jesús Jiménez-Barbero,3 and Juan Luis Asensio1Email: lmontalvillo@iqog.csic.esNowadays it has become clear that CH/π interactions play a key role in a variety of molecular recognition processes including conformation stabilization, crystal packing, formation of gas phase clusters, or chiral discrimination. Nevertheless, there are still aspects of these interactions that remain poorly understood.Figure 1. Effect of CH polarization (A and B) on the stability of CH/π complexes in gas phase, together with those expected in water. The influence of water solvation on the stability of OH/π complexes (C) is also represented for comparison.Thus, electrostatic and charge-transfer contributions to CH/π complexes can be modulated by the attachment of electron-withdrawing substituents to the carbon atom leading to a stabilization of the complex in gas phase. Intriguingly, the outcome of this simple chemical modification in water is more difficult to predict. In fact, exposed R-OH/π contacts are usually highly destabilized in water due to the competence provided by the stronger and ubiquitous ROH/H2O conventional hydrogen bonds. Following a similar reasoning, the polarization of a particular CH could also enhance its own polar interactions with the solvent, thus leading to a minor stabilization, a null effect, or even a significant destabilization of the CH/π bonds. However, to the best of our knowledge, no unambiguous experimental evidences have been presented so far to support the stabilizing role of CH polarization in water. These questions have evident implications in the molecular recognition and drug design fields.Our work provides an unambiguous and quantitative answer to this question employing a simple strategy based on dynamic combinatorial chemistry that is of general relevance for different fields of chemistry and biology. [1][1] Jiménez-Moreno, E.; Gómez, A. M.; Bastida, A.; Corzana, F.; Jiménez-Oses, G.; Jiménez-Barbero, J.;Asensio, J. L. Angew. Chem. Int. Ed., 2015, 54, 4344.Acknowledgements: The authors are grateful to Ministerio de Economia y Competitividad for grant CTQ2013-45538-P.P

English

A dynamic combinatorial chemistry approach to quantify the contribution of electrostatics to the stability of CH/Π bonds in water

A dynamic combinatorial chemistry approach to quantify the contribution of electrostatics to the stability of CH/Π bonds in water

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