Hui Sun, Jinghua Li, Dongju Zhang
Mar 1, 2008
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Influential Citations
15
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Journal
Journal of Physical Organic Chemistry
Abstract
Smiles rearrangement (SR) falls under a broad category of organic synthesis for many important compounds. A complete understanding toward SR process appeals to the assistance of theoretical research. Herein, by performing quantum chemistry calculations, we give a theoretical evidence for the mechanism of a representative O–N type SR, the intramolecular cyclization of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide anion. It is found that the SR to the ipso-position involves a two-step mechanism and is energetically more favorable than the direct nucleophilic attack by N atom on the ortho-position. The present result rationalizes well the experimentally observed ipso-SR product and provides a consistent picture of the O–N SR process. Copyright © 2008 John Wiley & Sons, Ltd.