Synthesis and oxidation of 'non-annulated' vitamin E-like compounds

Thomas Rosenau; Amnon Stanger

doi:10.1016/j.tetlet.2005.09.009

Synthesis and oxidation of 'non-annulated' vitamin E-like compounds

Research output: Contribution to journal › Article › peer-review

Abstract

Two model compounds (3 and 4) having the typical α-tocopherol-type substitution pattern of the aromatic ring, but lacking the annulated pyran ring, have been synthesized. Upon oxidation, the two possible ortho-quinone methides (oQMs) of each are formed in equal ratio. DFT calculations suggest that there is no angular strain in 3 and 4, and each of the oQM pairs is of similar energy. These results prove that the commonly observed regioselectivity in oxidations of vitamin E-type model compounds is not an electronic substitution effect, but a consequence of annulation.

Original language	English
Pages (from-to)	7845-7848
Number of pages	4
Journal	Tetrahedron Letters
Volume	46
Issue number	45
DOIs	https://doi.org/10.1016/j.tetlet.2005.09.009
State	Published - 7 Nov 2005

Keywords

Antioxidants
Mills-Nixon effect
SIBL
Strain-induced bond localization
Tocopherol
Vitamin E

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2005.09.009

Cite this

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title = "Synthesis and oxidation of 'non-annulated' vitamin E-like compounds",

abstract = "Two model compounds (3 and 4) having the typical α-tocopherol-type substitution pattern of the aromatic ring, but lacking the annulated pyran ring, have been synthesized. Upon oxidation, the two possible ortho-quinone methides (oQMs) of each are formed in equal ratio. DFT calculations suggest that there is no angular strain in 3 and 4, and each of the oQM pairs is of similar energy. These results prove that the commonly observed regioselectivity in oxidations of vitamin E-type model compounds is not an electronic substitution effect, but a consequence of annulation.",

keywords = "Antioxidants, Mills-Nixon effect, SIBL, Strain-induced bond localization, Tocopherol, Vitamin E",

author = "Thomas Rosenau and Amnon Stanger",

note = "Funding Information: The financial support by the Austrian Fonds zur F{\"o}rderung der wissenschaftlichen Forschung, Project P-17428 is gratefully acknowledged. The authors would like to thank Dr. Andreas Hofinger, Department of Chemistry at the University of Natural Resources and Applied Life Sciences (BOKU), Vienna, for recording the NMR spectra.",

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doi = "10.1016/j.tetlet.2005.09.009",

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TY - JOUR

T1 - Synthesis and oxidation of 'non-annulated' vitamin E-like compounds

AU - Rosenau, Thomas

AU - Stanger, Amnon

N1 - Funding Information: The financial support by the Austrian Fonds zur Förderung der wissenschaftlichen Forschung, Project P-17428 is gratefully acknowledged. The authors would like to thank Dr. Andreas Hofinger, Department of Chemistry at the University of Natural Resources and Applied Life Sciences (BOKU), Vienna, for recording the NMR spectra.

PY - 2005/11/7

Y1 - 2005/11/7

N2 - Two model compounds (3 and 4) having the typical α-tocopherol-type substitution pattern of the aromatic ring, but lacking the annulated pyran ring, have been synthesized. Upon oxidation, the two possible ortho-quinone methides (oQMs) of each are formed in equal ratio. DFT calculations suggest that there is no angular strain in 3 and 4, and each of the oQM pairs is of similar energy. These results prove that the commonly observed regioselectivity in oxidations of vitamin E-type model compounds is not an electronic substitution effect, but a consequence of annulation.

AB - Two model compounds (3 and 4) having the typical α-tocopherol-type substitution pattern of the aromatic ring, but lacking the annulated pyran ring, have been synthesized. Upon oxidation, the two possible ortho-quinone methides (oQMs) of each are formed in equal ratio. DFT calculations suggest that there is no angular strain in 3 and 4, and each of the oQM pairs is of similar energy. These results prove that the commonly observed regioselectivity in oxidations of vitamin E-type model compounds is not an electronic substitution effect, but a consequence of annulation.

KW - Antioxidants

KW - Mills-Nixon effect

KW - SIBL

KW - Strain-induced bond localization

KW - Tocopherol

KW - Vitamin E

UR - https://www.scopus.com/pages/publications/26444546355

U2 - 10.1016/j.tetlet.2005.09.009

DO - 10.1016/j.tetlet.2005.09.009

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AN - SCOPUS:26444546355

SN - 0040-4039

VL - 46

SP - 7845

EP - 7848

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 45

ER -

Synthesis and oxidation of 'non-annulated' vitamin E-like compounds

Abstract

Keywords

ASJC Scopus subject areas

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