Hydride Dissociation Energies of Six-Membered Heterocyclic Organic Hydrides Predicted by ONIOM-G4Method.
Summary of "Hydride Dissociation Energies of Six-Membered Heterocyclic Organic Hydrides Predicted by ONIOM-G4Method."
Hydride dissociation energy is of great importance in understanding the hydride-donating abilities of organic hydrides. Although the hydride dissociation energies of some organic hydrides have been experimentally measured, much less attention has been focused on the investigation of these quantities from the first principles of physics. Herein, we developed an ONIOM-G4 method and carefully benchmarked this new method against 48 experimental hydride dissociation energies of diverse bulky molecules. It was found that with the combined methods of the HF/6-31+G(d,p)//IEFPCM/Bondi1.15 solvation model, the ONIOM-G4 method can predict the hydride dissociation energies with an error bar of only 1.7 kcal/mol. With the newly developed ONIOM-G4 method, we then systematically studied the hydride dissociation energies of six categories of biologically and pharmaceutically important six-membered heterocyclic organic hydrides, namely, the organic hydrides containing 1,4-dihydropyridine, 1,4-dihydropyrazine, 1,4-oxazine, 1,4-thiazine, 4H-pyran, and 4H-thiopyran ring structures. An extensive hydride dissociation energy scale containing over 100 six-memebered heterocyclic organic hydrides has been established, which may find applications in both synthetic organic chemistry and mechanistic studies of various chemical or biological processes involving transferring of the hydride anion.
Affiliation
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Journal Details
This article was published in the following journal.
Name: Journal of chemical information and modeling
ISSN: 1549-960X
Pages: 63-75
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/22146106
- DOI: http://dx.doi.org/10.1021/ci2001567
Medical and Biotech [MESH] Definitions
Azepines
Seven membered heterocyclic rings containing a NITROGEN atom.
Azulenes
Compounds based on a seven-membered ring fused to a five-membered ring. Heat can rearrange them to NAPHTHALENES which have two fused six-membered rings. They are similar to guaiazulenes which are SESQUITERPENES with a six-membered ring fused to a five-membered ring.
Pyrazolones
Compounds with a five-membered heterocyclic ring with two nitrogens and a keto OXYGEN. Some are inhibitors of TNF-ALPHA production.
Oxazoles
Five-membered heterocyclic ring structures containing an oxygen in the 1-position and a nitrogen in the 3-position, in distinction from ISOXAZOLES where they are at the 1,2 positions.
Oxocins
Compounds based on an 8-membered heterocyclic ring including an oxygen. They can be considered medium ring ethers.
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