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QM and QM/MM studies of selectivity in organic and bioorganic chemistry
Author(s) -
Harvey Jeremy N.,
Aggarwal Varinder K.,
Bathelt Christine M.,
CarreónMacedo JoséLuis,
Gallagher Timothy,
Holzmann Nicole,
Mulholland Adrian J.,
Robiette Raphaël
Publication year - 2006
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1030
Subject(s) - chemistry , selectivity , steric effects , electrophile , combinatorial chemistry , bioorganic chemistry , electronic effect , computational chemistry , biphenyl , organic chemistry , stereochemistry , catalysis , enzyme
Electronic structure methods are used to explore the origin of selectivity in a number of organic, organometallic and bioorganic processes. Diastereoselectivity 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 © 2006 John Wiley & Sons, Ltd.