Nonbonded, attractive cation-pi interactions in azide-mediated asymmetric ring expansion reactions |
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Authors: | Katz Christopher E Ribelin Timothy Withrow Donna Basseri Yashar Manukyan Anna K Bermudez Amy Nuera Christian G Day Victor W Powell Douglas R Poutsma Jennifer L Aubé Jeffrey |
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Affiliation: | Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Room 2010, Malott Hall, Lawrence, Kansas 66045-7582, USA. |
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Abstract: | The influence of attractive, nonbonded interactions on the reactions of 1,2- and 1,3-hydroxyalkyl azides with ketones has been investigated through experimental and computational means. A series of 1,3-hydroxyalkyl azides bearing electronically tuned aromatic groups at the 2 position were prepared and reacted along with several derivatives designed to conformationally restrict the rotational orientation of the aromatic substituent. These studies showed that a cation-pi interaction between an aryl moiety and an N2(+) leaving group plays a role in determining the stereoselectivity of these reactions. A series of ab initio calculations supported this hypothesis. A computational and experimental analysis suggested a primarily steric model for the analogous reactions of substituted 2-azido-1-ethanol analogues. |
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