Nonbonded, Attractive Cation−π Interactions in Azide-Mediated Asymmetric Ring Expansion Reactions

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 a...

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Bibliographic Details
Published in:Journal of organic chemistry 2008-05, Vol.73 (9), p.3318-3327
Main 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
Format: Article
Language:English
Subjects:
Alkylation
Azides - chemistry
Carbon - chemistry
Cations - chemistry
Chemistry
Cyclization
Ethanol - chemistry
Exact sciences and technology
Gases - chemistry
Hydroxylation
Molecular Structure
Organic chemistry
Propane - chemistry
Solvents
Stereoisomerism
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo800222r