How Do Substrates Bind to a Bifunctional Thiourea Catalyst? A Vibrational CD Study on Carboxylic Acid Binding

Chemistry : a European Journal
Nora M Kreienborg, Christian Merten

Abstract

Knowledge about the active conformation of an asymmetric catalyst is highly valuable in order to understand its stereoinductive power, but spectroscopic access to these structures is often limited. For the example of Takemoto's bifunctional thiourea, we demonstrate the capability of VCD spectroscopy to characterize the conformational preferences of the catalyst with and without having a reactant bound to it. In particular we show that the binding orientation of carboxylic acids can easily be derived from a computationally guided analysis of the spectra. Moreover, we identify characteristic marker bands, which are only visible in the VCD spectra of the catalyst/acid mixtures but not in the corresponding IR spectra. Lastly, we also discuss the problem that the popular DFT functional M06-2X, which we found to perform exceptionally well in the calculations of vibrational frequencies for fluorinated molecules, predicts incorrect structures of the molecular clusters. We relate this poor performance in predicting the structure of the binding topologies to an overestimation of dispersive CH-π and π-π interactions, which occur due to a neglect of the solvent molecules in the clusters. VCD spectroscopy is thus shown to be a powerful tool...Continue Reading

References

Feb 14, 2002·Organic Letters·Peter R Schreiner, Alexander Wittkopp
Oct 16, 2003·Journal of the American Chemical Society·Tomotaka OkinoYoshiji Takemoto
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Feb 24, 2006·Angewandte Chemie·Mark S Taylor, Eric N Jacobsen
Dec 7, 2007·Journal of the American Chemical Society·Stephan J Zuend, Eric N Jacobsen
Jan 21, 2012·Chemistry : a European Journal·Gábor TárkányiSzilárd Varga
Nov 30, 2012·Angewandte Chemie·Katrien Brak, Eric N Jacobsen
Jan 11, 2014·Physical Chemistry Chemical Physics : PCCP·Monika ObrzudAleksander Koll
Jun 24, 2015·Angewandte Chemie·Christian MertenBenjamin List
Apr 27, 2017·Organic Letters·Lisa M SchneiderMathias Christmann
Jun 1, 2017·Physical Chemistry Chemical Physics : PCCP·Christian Merten

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Citations

Dec 25, 2019·Physical Chemistry Chemical Physics : PCCP·Luisa WeirichChristian Merten
Jul 4, 2020·Physical Chemistry Chemical Physics : PCCP·Tom Vermeyen, Christian Merten
Apr 21, 2021·Physical Chemistry Chemical Physics : PCCP·Sarah Karbalaei KhaniChristof Hättig
Jun 12, 2021·Physical Chemistry Chemical Physics : PCCP·Luisa Weirich, Christian Merten
Nov 4, 2021·Physical Chemistry Chemical Physics : PCCP·Tino P Golub, Christian Merten

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