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Theoretical evidence on O–N type smiles rearrangement mechanism: a computational study on the intramolecular cyclization of N ‐methyl‐2‐(2‐chloropyridin‐3‐yloxy)‐acetamide anion
Author(s) -
Sun Hui,
Li Jinghua,
Zhang Dongju,
Ma Chen,
Liu Chengbu
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1298
Subject(s) - chemistry , smiles rearrangement , acetamide , intramolecular force , mechanism (biology) , ion , medicinal chemistry , stereochemistry , computational chemistry , organic chemistry , philosophy , epistemology
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.