Journal article

Publication year: 2017

Pages: 71-76

Journal: Nature Chemistry

Volume number: 9

DOI Link: https://doi.org/10.1038/nchem.2609

Publisher: Nature Research

Abstract: 

Conformational control of organic reactions is at the heart of the biomolecular sciences. To achieve a particular reactivity, one of many conformers may be selected, for instance, by a (bio)catalyst, as the geometrically most suited and appropriately reactive species. The equilibration of energetically close-lying conformers is typically assumed to be facile and less energetically taxing than the reaction under consideration itself: this is termed the ‘Curtin–Hammett principle’. Here, we show that the trans conformer of trifluoromethylhydroxycarbene preferentially rearranges through a facile quantum-mechanical hydrogen tunnelling pathway, while its cis conformer is entirely unreactive. Hence, this presents the first example of a conformer-specific hydrogen tunnelling reaction. The Curtin–Hammett principle is not applicable, due to the high barrier between the two conformers.

Harvard Citation style: Mardyukov, A., Quanz, H. and Schreiner, P. (2017) Conformer-specific hydrogen atom tunnelling in trifluoromethylhydroxycarbene, Nature Chemistry, 9, pp. 71-76. https://doi.org/10.1038/nchem.2609

APA Citation style: Mardyukov, A., Quanz, H., & Schreiner, P. (2017). Conformer-specific hydrogen atom tunnelling in trifluoromethylhydroxycarbene. Nature Chemistry. 9, 71-76. https://doi.org/10.1038/nchem.2609