A Hypersensitive Mechanistic Probe for Distinguishing between Radical and Carbocation Intermediates

Newcomb, Martin; Chestney, Daryl L.

doi:10.1021/ja00100a052

Cited by 61 publications

(41 citation statements)

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“…Newcomb and Chestney, 1994; Auclair et al, 2002; Newcomb et al, 2003). In the conventional P450 reaction and in the HPL-CYP74 reaction, it is possible to envisage elements of both radical and ionic mechanisms in the pathway to products.…”

Section: Mechanism Of Hpl: a Purely Radical Pathway?mentioning

confidence: 99%

Mechanistic aspects of CYP74 allene oxide synthases and related cytochrome P450 enzymes

2009

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The existence of CYP5, CYP8A, and the CYP74 enzymes specialized for reaction with fatty acid peroxide substrates presents opportunities for a "different look" at the catalytic cycle of the cytochrome P450s. This review considers how the properties of the peroxide-metabolizing enzymes are distinctive, and how they tie in with those of the conventional monooxygenase enzymes. Some unusual reactions of each class have parallels in the other. As new enzyme reactions and new P450 structures emerge there will be possibilities for finding their special properties and edging this knowledge into the big picture.

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Section: Mechanism Of Hpl: a Purely Radical Pathway?mentioning

confidence: 99%

Mechanistic aspects of CYP74 allene oxide synthases and related cytochrome P450 enzymes

2009

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“…Alternate mechanistic proposals involving FeO 2 (H) as the reactive oxidant and also more concerted or carbocation mechanisms have also been presented [19,20]. The reader is referred elsewhere for further discussion of these possibilities [8,21,22].…”

Section: Figurementioning

confidence: 99%

Mechanisms of cytochrome P450 substrate oxidation: MiniReview

Guengerich¹

2007

J Biochem & Molecular Tox

210

177

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Cytochrome P450 (P450) enzymes catalyze a variety of oxidation and some reduction reactions, collectively involving thousands of substrates. A general chemical mechanism can be used to rationalize most of the oxidations and involves a perfenyl intermediate (FeO 3+ ) and odd-electron chemistry, i.e. abstraction of a hydrogen atom or electron followed by oxygen rebound and sometimes rearrangement. This general mechanism can explain carbon hydroxylation, heteroatom oxygenation and dealkylation, epoxidation, desaturation, heme destruction, and other reactions. Another approach to understanding catalysis involves analysis of the more general catalytic cycle, including substrate specificity, because complex patterns of cooperativity are observed with several P450s. Some of the complexity is due to slow conformational changes in the proteins that occur on the same timescale as other steps. C 2007 Wiley Periodicals, Inc.

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“…As in previous works, [2][3][4] 1-Methyl-2-phenylindane 6 and (E)-1,2-diphenyl-2-butene 8 were isolated from reaction mixtures (see experimental part). 2-phenyltetralin 7 was isolated among other reaction products, this structure was proposed by NMR ( 1 H, 13 C) and GC-MS comparisons with literature and database data (NIST98.L).…”

Section: Methodsmentioning

confidence: 91%

“…13,14 In mechanistic studies involving 6-halo-1-heptenes, this information was provided by the proportion of cis-and trans-isomers of the 1,2-dimethylcyclopentane obtained. The 6-hepten-2-yl radical cyclizes with a preference for the cis-stereochemistry while the corresponding organolithium gives predominantly the trans-isomer.…”

Section: Methodsmentioning

confidence: 99%

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

Reynaud¹,

Hazimeh²,

Mattalia³

et al. 2011

Arkivoc

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The o-(3-butenyl)phenyl system bearing a phenyl group on the 2-position of the side chain was studied as a potential mechanistic probe for distinguishing between radical and carbanion intermediates. The Bu3SnH reduction of 1-bromo-2-(2-phenyl-3-butenyl)benzene, 4, yields mainly the 1,5-cyclization product, 6, with a preference for the trans-isomer. Treatment of 4 with Mg or t-BuLi leads to double-bond isomerization and yields (E)-1,2-diphenyl-2-butene, 8, along with 3,4-diphenyl-1-butene, 5.

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A Hypersensitive Mechanistic Probe for Distinguishing between Radical and Carbocation Intermediates

Cited by 61 publications

References 0 publications

Mechanistic aspects of CYP74 allene oxide synthases and related cytochrome P450 enzymes

Mechanistic aspects of CYP74 allene oxide synthases and related cytochrome P450 enzymes

Mechanisms of cytochrome P450 substrate oxidation: MiniReview

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

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