Vitamin E models. Shortened sidechain models of α, β, γ and δ tocopherol and tocotrienol - A density functional study

David H. Setiadi, Gregory A. Chass, Ladislaus L. Torday, A. Varró, J. Papp

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Model compounds of α-, β-, γ-, and δ-tocopherol and Tocotrienol, as well as their sulphur and selenium congeners, were subjected to density functional analysis. The mono methyl substitution either stabilized or destabilized the ring structures to a small extent as assessed in terms of isodesmic reactions. In general, multiple methyl substitutions destabilized the ring. Dimethyl para-substitution results in electronic stabilization and steric repulsion being nearly additive. This was not the case for ortho-dimethyl derivatives, whereby steric repulsions dominate; the meta-substituted models reflect the same trend to a lesser degree. Structurally, the phenolic hydroxyl orientation was approximately planar, with the hydroxyl proton oriented away from the adjacent Me group whenever the structure permitted such an orientation.

Original languageEnglish
Pages (from-to)11-26
Number of pages16
JournalJournal of Molecular Structure: THEOCHEM
Volume637
DOIs
Publication statusPublished - Oct 3 2003

Fingerprint

Tocotrienols
tocopherol
Tocopherols
Vitamins
Vitamin E
Hydroxyl Radical
Substitution reactions
substitutes
Selenium
Sulfur
functional analysis
congeners
Protons
Functional analysis
ring structures
selenium
sulfur
Stabilization
stabilization
Derivatives

Keywords

  • Density functional theory
  • Methyl substitution
  • Orientation of phenolic OH
  • Tocopherol
  • Tocotrienol

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Vitamin E models. Shortened sidechain models of α, β, γ and δ tocopherol and tocotrienol - A density functional study. / Setiadi, David H.; Chass, Gregory A.; Torday, Ladislaus L.; Varró, A.; Papp, J.

In: Journal of Molecular Structure: THEOCHEM, Vol. 637, 03.10.2003, p. 11-26.

Research output: Contribution to journalArticle

@article{584c3bb38ce440bb884ad9396dc6e334,
title = "Vitamin E models. Shortened sidechain models of α, β, γ and δ tocopherol and tocotrienol - A density functional study",
abstract = "Model compounds of α-, β-, γ-, and δ-tocopherol and Tocotrienol, as well as their sulphur and selenium congeners, were subjected to density functional analysis. The mono methyl substitution either stabilized or destabilized the ring structures to a small extent as assessed in terms of isodesmic reactions. In general, multiple methyl substitutions destabilized the ring. Dimethyl para-substitution results in electronic stabilization and steric repulsion being nearly additive. This was not the case for ortho-dimethyl derivatives, whereby steric repulsions dominate; the meta-substituted models reflect the same trend to a lesser degree. Structurally, the phenolic hydroxyl orientation was approximately planar, with the hydroxyl proton oriented away from the adjacent Me group whenever the structure permitted such an orientation.",
keywords = "Density functional theory, Methyl substitution, Orientation of phenolic OH, Tocopherol, Tocotrienol",
author = "Setiadi, {David H.} and Chass, {Gregory A.} and Torday, {Ladislaus L.} and A. Varr{\'o} and J. Papp",
year = "2003",
month = "10",
day = "3",
doi = "10.1016/S0166-1280(02)00597-3",
language = "English",
volume = "637",
pages = "11--26",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",

}

TY - JOUR

T1 - Vitamin E models. Shortened sidechain models of α, β, γ and δ tocopherol and tocotrienol - A density functional study

AU - Setiadi, David H.

AU - Chass, Gregory A.

AU - Torday, Ladislaus L.

AU - Varró, A.

AU - Papp, J.

PY - 2003/10/3

Y1 - 2003/10/3

N2 - Model compounds of α-, β-, γ-, and δ-tocopherol and Tocotrienol, as well as their sulphur and selenium congeners, were subjected to density functional analysis. The mono methyl substitution either stabilized or destabilized the ring structures to a small extent as assessed in terms of isodesmic reactions. In general, multiple methyl substitutions destabilized the ring. Dimethyl para-substitution results in electronic stabilization and steric repulsion being nearly additive. This was not the case for ortho-dimethyl derivatives, whereby steric repulsions dominate; the meta-substituted models reflect the same trend to a lesser degree. Structurally, the phenolic hydroxyl orientation was approximately planar, with the hydroxyl proton oriented away from the adjacent Me group whenever the structure permitted such an orientation.

AB - Model compounds of α-, β-, γ-, and δ-tocopherol and Tocotrienol, as well as their sulphur and selenium congeners, were subjected to density functional analysis. The mono methyl substitution either stabilized or destabilized the ring structures to a small extent as assessed in terms of isodesmic reactions. In general, multiple methyl substitutions destabilized the ring. Dimethyl para-substitution results in electronic stabilization and steric repulsion being nearly additive. This was not the case for ortho-dimethyl derivatives, whereby steric repulsions dominate; the meta-substituted models reflect the same trend to a lesser degree. Structurally, the phenolic hydroxyl orientation was approximately planar, with the hydroxyl proton oriented away from the adjacent Me group whenever the structure permitted such an orientation.

KW - Density functional theory

KW - Methyl substitution

KW - Orientation of phenolic OH

KW - Tocopherol

KW - Tocotrienol

UR - http://www.scopus.com/inward/record.url?scp=0141756067&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0141756067&partnerID=8YFLogxK

U2 - 10.1016/S0166-1280(02)00597-3

DO - 10.1016/S0166-1280(02)00597-3

M3 - Article

AN - SCOPUS:0141756067

VL - 637

SP - 11

EP - 26

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -