1,2,4-triazine vs. 1,3- and 1,4-oxazinones in normal- and inverse-electron-demand hetero-diels-alder reactions: Establishing a status quo by computational analysis

Rooshenas, Parham, Hof, Kira, Schreiner, Peter R. and Williams, Craig M. (2011) 1,2,4-triazine vs. 1,3- and 1,4-oxazinones in normal- and inverse-electron-demand hetero-diels-alder reactions: Establishing a status quo by computational analysis. European Journal of Organic Chemistry, 2011 5: 983-992. doi:10.1002/ejoc.201001365


Author Rooshenas, Parham
Hof, Kira
Schreiner, Peter R.
Williams, Craig M.
Title 1,2,4-triazine vs. 1,3- and 1,4-oxazinones in normal- and inverse-electron-demand hetero-diels-alder reactions: Establishing a status quo by computational analysis
Journal name European Journal of Organic Chemistry   Check publisher's open access policy
ISSN 1099-0690
1099-0690
Publication date 2011-02-01
Year available 2010
Sub-type Article (original research)
DOI 10.1002/ejoc.201001365
Volume 2011
Issue 5
Start page 983
End page 992
Total pages 10
Place of publication Weinheim, Germany
Publisher Wiley - VCH Verlag
Language eng
Formatted abstract
We present an analysis of the well-known normal- and inverse-electron-demand hetero-Diels–Alder reaction involving 1,2,4-triazine, 1,3-oxazin-6-one, and 1,4-oxazin-2-one, with alkenes and alkynes, utilizing density functional theory (DFT) at the SCS-MP2/cc-pVDZ//B3LYP/6-31G(d) level to establish a theoretical status quo for synthetic practioners regarding the relative reactivities and stereochemical outcomes for these useful heterocycles. The results suggest that in the unsubstituted cases 1,2,4-triazine is less reactive in comparison to 1,3-oxazin-6-one and 1,4-oxazin-2-one for both reaction modes, whereas the cycloaddition regioselectivities depend largely on the diene. For example, 1,3-oxazin-6-one leads to kinetic meta isomers, in comparison to 1,2,4-triazine and 1,4-oxazin-2-one, which give rise to para isomers.
Keyword Density functional calculations
Hetero-Diels–Alder reactions
Heterocycles
Oxazines
Triazines
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Article first published online: 22 DEC 2010

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 17 Feb 2012, 21:32:32 EST by Lucy O'Brien on behalf of School of Chemistry & Molecular Biosciences