117547-12-3Relevant academic research and scientific papers
Nonbonded, attractive cation-π interactions in azide-mediated asymmetric ring expansion reactions
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.,Aube, Jeffrey
, p. 3318 - 3327 (2008/09/20)
(Chemical Equation Presented) 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-π 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.
