QM and QM/MM studies of selectivity in organic and bioorganic chemistry
(2006) Journal of Physical Organic Chemistry — Vol. 19, n° 8-9, p. 608-615 (2006)
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- Authors
- Abstract
- Electronic structure methods are used to explore the origin of selectivity in a number of organic, organometallic and bioorganic processes. Diastereosellectivity in reactions of sulfur and phosphorus ylides is shown to arise during a variety of different elementary steps, and is due to steric and electronic effects. Unusual rearranged products from Heck reaction of o-bromo biphenyl derivatives are shown to result from an unusual electrophilic addition step. Predicting selectivity in oxidation of aromatic substrates by cytochrome P450 isoforms is a challenging problem, which can be tackled using hybrid QM/MM methods. Differences in the electronic structure of the Compound I active intermediates of different cytochrome P450 isoforms do not appear to be large enough to explain the different selectivity of these different isoforms. Copyright (c) 2006 John Wiley & Sons, Ltd.
- Affiliations
University of Bristol School of Chemistry
Citations
Harvey, J., Aggarwal, V. K., Bathelt, C. M., Carreon-Macedo, J. L., Gallagher, T., Holzmann, N., Mulholland, A. J., & Robiette, R. (2006). QM and QM/MM studies of selectivity in organic and bioorganic chemistry. Journal of Physical Organic Chemistry, 19(8-9), 608-615. https://doi.org/10.1002/poc.1030 (Original work published 2006)