Open AccessThe Outcome of the Oxidations of Unusual Enediamide Motifs Is Governed by the Stabilities of the Intermediate Iminium Ions
Author(s) -
Muneer Ahamed,
Bun Chan,
Paul R. Jensen,
Matthew H. Todd
Publication year - 2012
Publication title -
plos one
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.99
H-Index - 332
ISSN - 1932-6203
DOI - 10.1371/journal.pone.0047224
Subject(s) - iminium , chemistry , ring (chemistry) , ion , bond cleavage , cleavage (geology) , crystallography , stereochemistry , double bond , computational chemistry , photochemistry , polymer chemistry , materials science , organic chemistry , catalysis , fracture (geology) , composite material
We compare the results from the oxidation of two unusual “enediamide” motifs (3,4-dihydropyrazin-2(1 H )-ones), where a double bond is flanked by two amides. In one case the oxidation led to a ring-opened product arising from the cleavage of the double bond, and in the other a rare cis -dioxygenated compound was obtained. Both products have been characterized by X-ray crystallography. The outcomes of the key reactions are rationalized based on calculated free energies of intermediates.