Synthetically useful metal-mediated radical transformations in water and aqueous media

Postigo, Al; Nudelman, Norma Sbarbati

doi:10.1016/j.ccr.2011.07.015

Cited by 24 publications

(24 citation statements)

References 283 publications

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“…1B). We were encouraged by reports of water-based organic reactions in which an alkene group functions as a radical acceptor (19). Knowing that Dha could function as a radical acceptor, we chose alkyl radicals that can be generated from alkyl iodides by transition metals (19).…”

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confidence: 99%

“…We were encouraged by reports of water-based organic reactions in which an alkene group functions as a radical acceptor (19). Knowing that Dha could function as a radical acceptor, we chose alkyl radicals that can be generated from alkyl iodides by transition metals (19). Inspired by recent metal-mediated conjugate addition reactions (20), we reasoned that organozinc species would form from the precursor halides and Zn metal.…”

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confidence: 99%

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A chemical biology route to site-specific authentic protein modifications

Yang

Ahn

et al. 2016

Science

216

198

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Many essential biological processes are controlled by posttranslational protein modifications. The inability to synthetically attain the diversity enabled by these modifications limits functional studies of many proteins. We designed a three-step approach for installing authentic posttranslational modifications in recombinant proteins. We first use the established O-phosphoserine (Sep) orthogonal translation system to create a Sep-containing recombinant protein. The Sep residue is then dephosphorylated to dehydroalanine (Dha). Last, conjugate addition of alkyl iodides to Dha, promoted by zinc and copper, enables chemoselective carbon-carbon bond formation. To validate our approach, we produced histone H3, ubiquitin, and green fluorescent protein variants with site-specific modifications, including different methylations of H3K79. The methylated histones stimulate transcription through histone acetylation. This approach offers a powerful tool to engineer diverse designer proteins.

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confidence: 99%

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A chemical biology route to site-specific authentic protein modifications

Yang

Ahn

et al. 2016

Science

216

198

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“…[11][12][13][14] Two effective radical perfluoroalkylations of some electron-deficient alkenes have been recently described: one affords the synthesis of chiral fluorinated aminoacids and peptides, and the other is based on the addition of perfluoroalkyl iodides to electron-deficient alkenes using aqueous 23 We have recently reviewed many non-carbon-centered radicals that are used in water to induce and accomplish several synthetically useful organic transformations. 24 Herewith, we describe a novel and easy methodology for the synthesis of perfluoroalkyl compounds, based on a radical reaction under thermal initiation by ACCN. This synthesis uses water as solvent; it circumvents the use of transition metals as catalysts and of pollutant organic solvents.…”

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confidence: 99%

Perfluoroalkylation of alkenes and alkynes in water

Vázquez¹,

Nudelman²

2015

Arkivoc

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Perfluoroalkylation of alkenes and alkynes was performed using thermal initiation by ACCN (1,1'-azobis(cyclohexanecarbonitrile)) in water, with good yields. The procedure is simple and more ecofriendly that most of the methods published for the synthesis of related compounds. Using water (without any cosolvent or metal catalysts), it allows the synthesis of the addition products with medium to high yields.

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“…Also, (Me 3 Si) 3 SiH was recently used in water, proving an excellent H-donor in this medium [1]. In some of the latter experiments the chemical yields in water were better than in an organic solvent.Radical substitution reactions in aqueous environment employing metallic species have been recently reviewed [2,3]. Electrontransfer substitution reactions in aqueous media have also been recently discussed in the literature [4].…”

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confidence: 99%

“…Radical substitution reactions in aqueous environment employing metallic species have been recently reviewed [2,3]. Electrontransfer substitution reactions in aqueous media have also been recently discussed in the literature [4].…”

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confidence: 99%

Photoinduced Electron Transfer-Mediated Substitutions in Aqueous Media

Martin-Flesia¹,

Postigo

2012

COC

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This account intends to cover recent literature on photoinduced substitution reactions in water or aqueous media with synthetic utility.Interesting synthetic targets, such as benzothiazine rings, benzoxazoles, aromatic photosubstitutions on 6-fluoroquinoles, can be accomplished in a benign aqueous environment, reducing the impact of organic solvents, or the use of metals for substitution reactions.Synthetically-useful electron-transfer substitution reactions performed in aqueous media are noteworthy and not much developed. These reactions performed either through radicals or radical ion intermediates generated photochemically in aqueous environment will prove convenient and alternative sustainable options at hand for the organic synthetic chemist. Metal-mediated photoinduced electron transfer reactions will not be dealt with in this account, as have been the subject of recent review articles, as is the case of radical perfluoroalkylation substitution reactions in aqueous media which have been recently summarized.Keywords: Photocyclization in aqueous media, PET-in aqueous media, Photosubstitution in aqueous media.Radicals and radical ion species in organic synthesis have been invoked increasingly during the last two decades accounting for many methods of carbon-carbon bond formation. Thus, carboncarbon bond formation via carbon-centered radicals or through photoinduced electron transfer reactions (PET) is regarded as a useful choice available to the synthetic chemists. These routes have the advantage of tolerating the presence of water, and therefore reducing the environmental impact on synthesis. In this class of reactions, photoinduced addition and substitutions play important synthetic roles. For more than a century, carbon-carbon bond formation in aqueous media has been virtually limited to electrochemical processes and aldol condensation reactions. Using radicals and radical ions in water or a water-containing mixed solvents reduces the use of toxic or dangerous environments, simplifies the work-up (often a simple extraction), and takes advantage of the specific effects occurring in water, such as hydrogen-bonding. Only very recently were radicals employed in the formation of carboncarbon bonds in aqueous media [1]. Such reactions were usually carried out through some modification of the usual methods of generation of radicals e.g. through hydrosoluble initiators, the Et 3 B/O 2 method and H 3 PO 2 as the reducing agent. Also, (Me 3 Si) 3 SiH was recently used in water, proving an excellent H-donor in this medium [1]. In some of the latter experiments the chemical yields in water were better than in an organic solvent.Radical substitution reactions in aqueous environment employing metallic species have been recently reviewed [2,3]. Electrontransfer substitution reactions in aqueous media have also been recently discussed in the literature [4]. However, syntheticallyuseful electron-transfer photosubstitution (PET-substitution) reactions performed in aqueous media are noteworthy and not much developed.This acco...

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Synthetically useful metal-mediated radical transformations in water and aqueous media

Cited by 24 publications

References 283 publications

A chemical biology route to site-specific authentic protein modifications

A chemical biology route to site-specific authentic protein modifications

Perfluoroalkylation of alkenes and alkynes in water

Photoinduced Electron Transfer-Mediated Substitutions in Aqueous Media

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