The Free-Radical Chemistry of Cyclic Ethers. V. β-Hydrogen Atom Abstraction from Epoxides and a Thioepoxide

Sabatino, Edward C.; Gritter, Roy J.

doi:10.1021/jo01047a038

Cited by 36 publications

(12 citation statements)

References 2 publications

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“…Treatment of propylene sulfide with di-/-butyl peroxide affords, among other products, thioacetone (415). Treatment of propylene sulfide with di-/-butyl peroxide affords, among other products, thioacetone (415).…”

Section: Ph Phmentioning

confidence: 99%

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Free-Radical Rearrangements

Beckwith¹,

Ingold²

1980

Organic Chemistry: A Series of Monographs

114

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Section: Ph Phmentioning

confidence: 99%

“…The β scission of oxiranyl radicals has been more extensively studied (59,(414)(415)(416)(417)(418)(419). Electron spin resonance measurements (59,418,419) indi cate that the rates of formation of α-ketoalkyl radicals depend on the number and type of substituents.…”

Section: Ph Phmentioning

confidence: 99%

Free-Radical Rearrangements

Beckwith¹,

Ingold²

1980

Organic Chemistry: A Series of Monographs

114

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“…1. The interconversion of allyloxy radicals and epoxy carbinyl radicals[23–25] (the C–O bond formation and cleavage) is one of the fastest known radical reactions[26] (k 1 = 2 × 10 9 s −1 , k −1 = 3.2 × 10 10 s −1 , respectively[27, 28]). C–C bond cleavage of epoxy carbinyl radicals is also known but only if the substrate has radical-stabilizing groups, e.g., phenyl or vinyl.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation of a linoleate-derived γ-hydroperoxy-α,β-unsaturated epoxide to γ-hydroxy- and γ-oxo-alkenals involves a unique pseudo-symmetrical diepoxycarbinyl radical

Salomon

2012

Free Radical Biology and Medicine

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Many of the pathological effects of lipid peroxidation are mediated by aldehydes generated through fragmentation of lipid peroxides. Among these aldehydes, the γ-hydroxy- and γ-oxo-α,β-alkenals, e.g., 4-hydroxy-2-nonenal (HNE), and 4-oxo-2-nonenal (ONE), are especially prone to modify proteins and DNA through covalent adduction. In addition the “mirror image” γ-hydroxy- and γ-oxo- α,β-alkenal phospholipids, can serve as high affinity ligands for biological receptors triggering pathology. Therefore, the mechanisms by which these aldehydes are generated in vivo are under intense scrutiny. We now report observations supporting the intermediacy of a unique pseudo symmetrical diepoxycarbinyl radical that accounts for the coproduction of HNE, ONE and their “mirror image” analogues 9-hydroxy-12-oxo-dodec-10-enoic acid (HODA), 9-keto-12-oxo-dodec-10-enoic acid (KODA) upon fragmentation of 13-hydroperoxy-cis-9,10-epoxyoctadeca-11-enoic acid (13-HP-Epo-Acid).

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“…The first opening of a heterocycle through free‐radical chemistry was reported in 1963. Epoxycarbinyl radicals, which were generated through hydrogen‐atom abstraction from epoxides, were found to undergo CO bond cleavage to give an allyloxy radical (Scheme ) 3. The analogy to the opening of the cyclopropylcarbinyl radical was immediately recognized 2c…”

Section: Epoxide Oxetane and Aziridine Opening Through Generatiomentioning

confidence: 99%

“…The first attempts to use alkoxyl radicals in reactions other than their simple reduction3, 4 involved 5‐ exo and 6‐ exo cyclizations to yield tetrahydrofurans and tetrahydropyrans (Scheme ) 19. More elaborate tandem sequences have led to numerous applications.…”

Section: Epoxide Oxetane and Aziridine Opening Through Generatiomentioning

confidence: 99%

Strained Heterocycles in Radical Chemistry

2003

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Over the last few decades the use of radicals in synthesis has witnessed an explosive growth through introduction of efficient chain and electron-transfer reactions. Strained heterocycles, in particular, have emerged as a highly versatile and readily available class of radical precursors. The generation of carbinyl radicals of heterocycles has resulted in many elegant applications of heteroatom-centered radicals, such as beta fragmentations, cyclizations, and intramolecular hydrogen atom abstractions. Direct electron transfer to strained heterocycles has been realized through the use of arene radical anions. The method combines the virtues of radical and organometallic chemistry to yield useful functionalized organolithium compounds. Epoxides have been opened with high regioselectivity by titanocene(III) reagents in either stoichiometric or catalytic quantities to yield beta-titanoxy radicals. This development has resulted in many new applications in natural product synthesis.

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The Free-Radical Chemistry of Cyclic Ethers. V. β-Hydrogen Atom Abstraction from Epoxides and a Thioepoxide

Cited by 36 publications

References 2 publications

Free-Radical Rearrangements

Free-Radical Rearrangements

Fragmentation of a linoleate-derived γ-hydroperoxy-α,β-unsaturated epoxide to γ-hydroxy- and γ-oxo-alkenals involves a unique pseudo-symmetrical diepoxycarbinyl radical

Strained Heterocycles in Radical Chemistry

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