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Transformation of α-Tocopherol (Vitamin E) and Related Chromanol Model Compounds into Their Phenoxonium Ions by Chemical Oxidation with the Nitrosonium Cation

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Stephen B. Lee, Ching Yeh Lin, Peter M. W. Gill, and Richard D. Webster*

Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia

J. Org. Chem., 2005, 70 (25), pp 10466–10473

DOI: 10.1021/jo0517951

Publication Date (Web): November 16, 2005

Fax: + 61 2 6125 0750.

, webster@rsc.anu.edu.au

Abstract

α-Tocopherol (α-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO⁺SbF₆^- in CH₃CN at 233 K to form phenoxonium cations (α-TO⁺SbF₆^-) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, ¹H and ¹³C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.

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Published In Issue December 09, 2005
Received August 26, 2005

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Article

Transformation of α-Tocopherol (Vitamin E) and Related Chromanol Model Compounds into Their Phenoxonium Ions by Chemical Oxidation with the Nitrosonium Cation