Single electron transfer in reactions of alkyl halides with lithium thiolates

Ashby, E. C.; Park, W. S.; Goel, A. B.; Su, Wei Yang

doi:10.1021/jo00225a041

Cited by 50 publications

(24 citation statements)

References 12 publications

(19 reference statements)

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“…5b) (38,39). Such a SET process would create SDHA, a known intermediate which as a stabilized radical gives rise to the powerful antioxidant properties of AA.…”

Section: Discussionmentioning

confidence: 99%

Functional Divergence in the Glutathione Transferase Superfamily in Plants

Dixon

Davis

Edwards

2002

Journal of Biological Chemistry

368

161

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Searches with the human Omega glutathione transferase (GST) identified two outlying groups of the GST superfamily in Arabidopsis thaliana which differed from all other plant GSTs by containing a cysteine in place of a serine at the active site. One group consisted of four genes, three of which encoded active glutathionedependent dehydroascorbate reductases (DHARs). Two DHARs were predicted to be cytosolic, whereas the other contained a chloroplast targeting peptide. The DHARs were also active as thiol transferases but had no glutathione conjugating activity. Unlike most other GSTs, DHARs were monomeric. The other class of GST comprised two genes termed the Lambda GSTs (GSTLs). The recombinant GSTLs were also monomeric and had glutathione-dependent thiol transferase activity. One GSTL was cytosolic, whereas the other was chloroplasttargeted. When incubated with oxidized glutathione, the putative active site cysteine of the GSTLs and cytosolic DHARs formed mixed disulfides with glutathione, whereas the plastidic DHAR formed an intramolecular disulfide. DHAR S-glutathionylation was consistent with a proposed catalytic mechanism for dehydroascorbate reduction. Roles for the cytosolic DHARs and GSTLs as antioxidant enzymes were also inferred from the induction of the respective genes following exposure to chemicals and oxidative stress.

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“…5b) (38,39). Such a SET process would create SDHA, a known intermediate which as a stabilized radical gives rise to the powerful antioxidant properties of AA.…”

Section: Discussionmentioning

confidence: 99%

Functional Divergence in the Glutathione Transferase Superfamily in Plants

Dixon

Davis

Edwards

2002

Journal of Biological Chemistry

368

161

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“…On the other hand, it is well known that the P-H system is a good hydrogen source for the carbon-centered radicals, and dicyclohexylphosphine has been used as a free radical trap [29]. We decided to carry out the reaction of p-nitrobenzyl bromide with sodium diisopropyl phosphite in THF in the presence of dicyclohexylphosphine.…”

Section: Resultsmentioning

confidence: 99%

The direct preparation of the esters ofp-nitrobenzylphosphonic acid fromp-nitrobenzyl halides

Witt

Rachoń

1996

Heteroat. Chem.

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“…Moreover, the role of the radical of DCHP, formed after hydrogen donation, has not been clearly established, and in some cases it has been proposed as the initiator of a propagation cycle. 4 On the other hand, when liquid ammonia is used as a solvent, the low temperature slows down the polar pathway and the ET path prevails under irradiation triggering a radical chain substitution reaction (S RN 1).…”

Section: Reactions Of Neopentyl Iodide (1a) Effect Of the Solvent Anmentioning

confidence: 99%

“…No evidence for this mechanistic pathway was observed with the bromide probe. 4 The effects of leaving groups, solvent, and hydrogen atom donors have been investigated in the reaction of BzCH(Me)¯ with 6-X-5,5-dimethyl-1-hexenes (X = I, Br, or OTs) in HMPA. 5 It is suggested that the reaction of the iodo derivative takes place in part with radicals as intermediates while the bromide and tosylate compounds appear to react via the S N 2 pathway.…”

Section: Introductionmentioning

confidence: 99%

Substitution reactions between arenethiolate anions and 1,3-dihalo-2,2-dimethylpropanes. Synthetic scope and mechanistic aspects

Peñéñory¹,

Barrionuevo²,

Argüello³

2011

Arkivoc

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The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2-naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good to excellent yields. For all the substrates studied the monosubstituted halogenated product is the intermediate or the main product depending on the nature of the second leaving group. Aryl cyclopropyl sulfides were found as side products and their yields strongly depend on the base concentration (tertBuOK). Finally, using neopentyl iodide as a model, the mechanism of these reactions was evaluated based on non-kinetic evidence, demonstrating that the reactions switch from S RN 1 to polar S N 2 according to the solvent employed.

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Single electron transfer in reactions of alkyl halides with lithium thiolates

Cited by 50 publications

References 12 publications

Functional Divergence in the Glutathione Transferase Superfamily in Plants

Functional Divergence in the Glutathione Transferase Superfamily in Plants

The direct preparation of the esters ofp-nitrobenzylphosphonic acid fromp-nitrobenzyl halides

Substitution reactions between arenethiolate anions and 1,3-dihalo-2,2-dimethylpropanes. Synthetic scope and mechanistic aspects

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