Journal article

Publication year: 2012

Pages: 11091-11095

Journal: The Journal of Organic Chemistry

Volume number: 77

Issue number: 24

DOI Link: https://doi.org/10.1021/jo302160s

Publisher: American Chemical Society

Abstract: 

Structure determination of reactive species is a key step in understanding reaction mechanisms. We demonstrate the application of polarization-dependent two-dimensional infrared spectroscopy (P2D-IR) as a powerful tool combining structure resolution with ultrafast time resolution. We apply this technique to investigate the substrate–catalyst complexes in a Lewis acid catalyzed Diels–Alder reaction. Using Mg(ClO₄)₂ as a Lewis acid, we found that an additional complex besides the chelate typically postulated as reactive species forms. Experimental access to this new species leads to a deeper understanding of the observed selectivities for the Diels–Alder reaction catalyzed by Lewis acids. Our findings are supported by density functional computations at the M06/6-31+G(d,p) level, including solvent corrections.

Harvard Citation style: Messmer, A., Steinwand, S., Lippert, K., Schreiner, P. and Bredenbeck, J. (2012) Ultrafast Two-Dimensional Infrared Spectroscopy Resolves the Conformational Change of an Evans Auxiliary Induced by Mg(ClO4)2, The Journal of Organic Chemistry, 77(24), pp. 11091-11095. https://doi.org/10.1021/jo302160s

APA Citation style: Messmer, A., Steinwand, S., Lippert, K., Schreiner, P., & Bredenbeck, J. (2012). Ultrafast Two-Dimensional Infrared Spectroscopy Resolves the Conformational Change of an Evans Auxiliary Induced by Mg(ClO4)2. The Journal of Organic Chemistry. 77(24), 11091-11095. https://doi.org/10.1021/jo302160s