From a theoretical concept to biochemical reactions: Strain-induced bond localization (SIBL) in oxidation of vitamin E

Chemistry - A European Journal

Volumn 11, Issue 1, 2005, Pages 280-287

  Rosenau, Thomas ^a   Ebner, Gerald ^a   Stanger, Amnon ^b   Perl, Sharon ^b   Nuri, Limor ^b  

^a UNIVERSITY OF NATURAL RESOURCES AND LIFE SCIENCES   (Austria)

^b TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

Density functional calculations; Mills Nixon effect; Natural products; Quinone methide; Strain induced bond localization (SIBL); Vitamins

Indexed keywords

ANNULATION ANGLES; BIOCHEMICAL REACTIONS; ORTHOQUINONE METHIDE (OQM); STRAIN-INDUCED BOND LOCALIZATION (SIBL);

BIOCHEMISTRY; DERIVATIVES; ISOMERS; MATHEMATICAL MODELS; OXIDATION; POSITIVE IONS; VITAMINS;

REACTION KINETICS;

ALPHA TOCOPHEROL DERIVATIVE; ANTIOXIDANT; BENZOFURAN DERIVATIVE; BENZOPYRAN DERIVATIVE; LITHIUM DERIVATIVE; METAL OXIDE; NATURAL PRODUCT; QUINONE METHIDE; SILVER; UNCLASSIFIED DRUG; VITAMIN;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; CRYSTALLIZATION; DENSITY FUNCTIONAL THEORY; MILLS NIXON EFFECT; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; TEMPERATURE;

ANTIOXIDANTS; MODELS, MOLECULAR; MOLECULAR CONFORMATION; OXIDATION-REDUCTION; STRESS, MECHANICAL; VITAMIN E;

EID: 19944429553     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400265     Document Type: Article

References (49)

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23. b) In addition to using a large excess of trapping agent present, it has been shown that the reaction with ethyl vinyl ether is faster than the dimerization of the oQMs, so that spiro-dimer formation in the presence of the trapping agent was negligible: T. Rosenau, A. Potthast, T. Elder, P. Kosma, Org. Lett. 2002, 4, 4285-4286.
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25. + is used as a counterion to the phenolate in 16, 17, and 18.
26. For the definition of SIBL (strain-induced bond localization) see: a) N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 542, 19-24; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 548, 113; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1998, 556, 249-250;
27. For the definition of SIBL (strain-induced bond localization) see: a) N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 542, 19-24; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 548, 113; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1998, 556, 249-250;
28. For the definition of SIBL (strain-induced bond localization) see: a) N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 542, 19-24; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1997, 548, 113; N. Ashkenazi, R. Boese, P. Stellberg, J. Organomet. Chem. 1998, 556, 249-250;
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35. A comparison of the total oxidation rates to 17 and 18 suggests that indeed 18 is not an intermediate: A. Stanger, S. Perl, L. Nuri, P. Kosma, T. Rosenau, unpublished results.
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41. One of the referees suggested that the relative rates can be correlated to the stability of the products. This is probably true, but cannot be used as evidence for the relative rates of the formation of the regioisomers.
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46. T. Rosenau, A. Potthast, A. Hofinger, P, Kosma, Angew. Chem. 2002, 114, 1219-1221; Angew. Chem. Int. Ed. 2002, 41, 1171-1173.
47. Available from earlier work: T. Rosenau, A. Potthast, T. Elder, T. Lange, H. Sixta, P. Kosma, J. Org. Chem. 2002, 67, 3607-3614. In short, 3-oxa-chromanols are obtained by treatment of trimethylhydroquinone with aliphatic aldehydes in acetic acid/HCl (cone.), v/v = 2:1.
48. The compound was available from earlier work, see reference [27]. In addition, it was obtained nearly quantitatively by dissolving trimethylhydroquinone and 3,3-dimethylcrotonic acid in the minimum amount of ethanol/HCl (cone.) (v/v = 10:1) and leaving the mixture several days in the fridge until no more product precipitated (ca. three weeks), followed by benzylation of the phenolic OH group with NaH/benzyl bromide in THF.
49. Detailed analytical data of the trapping products will be reported in due course.