Photosensitised oxidation of model unsaturated lipid systems: (4Z,7Z)-undeca-4,7-diene and (4Z)-undec-4-en-7-yne

Carless, H. A. J.; Batten, Richard

doi:10.1039/p19870001999

Cited by 34 publications

(20 citation statements)

References 10 publications

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“…All the products described so far were prepared in suffi cient amounts for NMR analysis, which revealed their covalent structures, and based on literature precedents, the relative stereochemistry of the carbon chain substituents of the endoperoxides in products 1 and 4 ( 17,18 ) ( Table 1 ).…”

Section: Structural Analysis Of Soybean Lox-1 Products 1-8mentioning

confidence: 99%

Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: a potential P450 and lipoxygenase interaction

Teder

Boeglin

Brash

2014

Journal of Lipid Research

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The oxygenation reactions of polyunsaturated fatty acids include several examples in which different enzymes collaborate in synthesis of the end product. The cyclooxygenases are paired with cytochrome P450s in the transformation of arachidonic acid to prostaglandin (PG) endoperoxides and on to thromboxane A 2 and prostacyclin ( 1, 2 ). A P450 and cyclooxygenase participate in the opposite order in the metabolism of P450-derived 8,9-epoxyeicosatrienoic acid (8,9-EET) by cyclooxygenase, giving epoxy-hydroxy products ( 3 ). The plant pathway of jasmonic acid synthesis involves initial oxygenation by a 13 S -lipoxygenase (LOX) followed by transformation to an allene oxide by the P450, CYP74 ( 2, 4 ). Other examples include the cooperation of LOX and peroxygenase enzymes in the formation of epoxy and hydroxy fatty acids ( 5-7 ). The present work describes a new type of interaction, not so far described in nature, yet with the potential to produce fatty acid hydroxy-endoperoxides. Further transformations could readily form triols or other derivatives.The impetus for the present work arose from further studies of fatty acid epoxidation by catalase-related enzymes primed with an oxygen donor, analogous to an earlier report of arachidonate and 8-HETE epoxidation by catalase-related allene oxide synthase ( 8 ). One example involved enzymatic epoxidation of 13 S -hydroxy-␣ -linolenic acid on the 15,16-double bond. To assign the confi guration of the new 15,16-epoxide group, we proposed a scheme using soybean LOX to introduce a 13 S -hydroperoxide into Abbreviations: AD1/AD2, 15,16-epoxy-linolenate enantiomers eluted from Chiralpak AD chiral column; EET, epoxyeicosatrienoic acid; HAc, glacial acetic acid; HPETE, hydroperoxyeicosatetraenoic acid; LOX, lipoxygenase; mCPBA, meta-chloroperoxybenzoic acid; P450, cytochrome P450; PG, prostaglandin; RP-HPLC, reversed phase HPLC; S N i, intramolecular nucleophilic substitution; SP-HPLC, straight phase HPLC; TPP, triphenylphosphine.

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Section: Structural Analysis Of Soybean Lox-1 Products 1-8mentioning

confidence: 99%

Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: a potential P450 and lipoxygenase interaction

Teder

Boeglin

Brash

2014

Journal of Lipid Research

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“…No product deriving from a 4-exo cyclization onto the double bond of the allylic tether was identified 157 . Additional examples illustrating the predominant formation of 3,5-cis-disubstituted 1,2-dioxolanes through radical cyclizations of homoallylic hydroperoxides were reported 163 . In the absence of particularly adverse factors, homoallylic peroxy-radicals undergo 5-exo-rather than 6-endo-cyclization 164 .…”

Section: Free Radical Cyclization Of Alkenyl Hydroperoxidesmentioning

confidence: 99%

Synthesis of Cyclic Peroxides

Korshin

Bachi

2009

Patai's Chemistry of Functional Groups

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“…5 Singlet oxygen can be generated in vivo through photosensitization 6 by retinal 7 in the eye as well as non photochemically. 8–10 β-Hydroperoxy alkylperoxides (Scheme 1, b ) are also produced by free radical cyclization of unsaturated peroxy radicals 11–13 formed during the autoxidation of PUFAs. 14,15 β-Hydroxy hydroperoxides (Scheme 1, c ) are also available through addition of H 2 O 2 to epoxides (Scheme 1, d ) 16–18 or through singlet oxygenation of allylic alcohols (Scheme 1, e ).…”

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confidence: 99%

Fragmentation of β-Hydroxy Hydroperoxides

Zhang

Salomon

2012

J. Org. Chem.

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A β-hydroxy hydroperoxide was obtained through base catalyzed disproportionation of a hydroperoxy endoperoxide available by singlet oxygenation of cyclohepta-1,4-diene. Vitamin E and C induce fragmentation of this β-hydroxy hydroperoxide generating aldehydes, especially in the presence of redox active metal ions such as those present in vivo, e.g., under conditions of “iron overload”. This chemistry may contribute to the oxidative cleavage of polyunsaturated fatty acyls that produces similar aldehydes, which damage proteins and DNA through covalent adduction resulting in “oxidative injury”.

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Photosensitised oxidation of model unsaturated lipid systems: (4Z,7Z)-undeca-4,7-diene and (4Z)-undec-4-en-7-yne

Cited by 34 publications

References 10 publications

Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: a potential P450 and lipoxygenase interaction

Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: a potential P450 and lipoxygenase interaction

Synthesis of Cyclic Peroxides

Fragmentation of β-Hydroxy Hydroperoxides

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