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Mechanism of Alkoxy Groups Substitution by Grignard Reagents on Aromatic Rings and Experimental Verification of Theoretical Predictions of Anomalous Reactions

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Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States
Department of Chemistry, One Shields Ave, University of California, Davis, California 95616, United States
Cite this: J. Am. Chem. Soc. 2013, 135, 17, 6633–6642
Publication Date (Web):March 26, 2013
https://doi.org/10.1021/ja4015937
Copyright © 2013 American Chemical Society

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    Abstract

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    The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone, and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated.

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    Additional figures, Cartesian coordinates, electronic energies, entropies, enthalpies, Gibbs free energies, lowest frequencies of the different conformations of all structures considered. This material is available free of charge via the Internet at http://pubs.acs.org.

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