Some Synthetic Uses of Halides

Hoyle, Jeff

doi:10.1002/9780470682531.pat0013

Cited by 4 publications

(4 citation statements)

References 946 publications

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“…Halogenated organic compounds are present in many pharmaceuticals and agrochemicals, with the halogens conferring biological properties via interaction with protein targets . Being considered as a potent inhibitor of pyruvate dehydrogenase kinases, but showing inactivity toward other protein kinases, α,α-dichloroacetophenone has attracted attention due to the biological significance as anticancer drug candidates as well as the synthetic potential as building blocks . As a result, α,α-dichloroketones have been pursued by chemical synthesis over the centuries.…”

Section: Introductionmentioning

confidence: 99%

Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

et al. 2022

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Precise control of the chemoselectivity of the halogenation of a substrate equipped with multiple nucleophilic sites is highly demanding and challenging. Most reported chlorinations of methyl ketones show poor compatibility or even exclusive selectivity toward electron-rich arene, olefin, and alkyne residues. This is attributed to the direct or in situ employment of electrophilic Cl 2 /Cl + species. Here, we reported that, even bearing those competitive residues, methyl ketones can still undergo dichlorination to afford α,α-dichloroketones in a chemo-specific manner. Enabled by the I 2 -dimethyl sulfoxide catalytic system, in which hydrochloric acid only acts as a nucleophilic Cl − donor, this straightforward dichlorination reaction is safe and operatorfriendly and has high atomic economy, giving access to structurally diverse α,α-dichloroketones in good yields and with good functional-group tolerance.

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Section: Introductionmentioning

confidence: 99%

Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

et al. 2022

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“…), while on the other hand, predictable and selective activation and, thus, functionalization can be achieved under alternative conditions (i.e., radical reactions, metal–halogen exchange, numerous other transition metals, nucleophilic substitution, etc. ). − This fact makes the carbon–halogen bond a major workhorse within organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…α-Haloketones are important intermediates in organic synthesis because of their high reactivity shown toward nucleophiles by both the electrophilic methylene and the carbonyl carbon atoms . They are key building blocks, valuable for the synthesis of a wide variety of biologically active heterocyclic compounds, , natural products, pesticides, diagnostic aids, and surfactants. ,, They serve as an important precursor for various transformations utilized in pharmaceutical synthesis .…”

Section: Introductionmentioning

confidence: 99%

Selenium Dioxide-Mediated Bromination of α,β-Unsaturated Ketones Using N-Bromosuccinimide in the Presence of p-Toluenesulfonic Acid: A Versatile Route for the Synthesis of α′-Bromo-4-arylbut-3-en-2-one and α′,α′-Dibromo-4-arylbut-3-en-2-one

et al. 2021

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An efficient method for the synthesis of α,β-unsaturated α′-bromoketones and α,β-unsaturated α′,α′-dibromoketones is described using N-bromosuccinimide (NBS) as the brominating agent mediated by selenium dioxide (SeO2) in the presence of p-toluenesulfonic acid (PTSA) monohydrate in toluene. The method is simple, employing easily available shelf reagents to afford a wide range of products in good yields. The method highlighted that simple fine-tuning of the reaction conditions and molar equivalents of the reactants easily affords either mono- or dibrominated products in excellent yields. A number of these products have not been reported in the literature. All of the reactions were carried out in gram-scale quantities.

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Some Synthetic Uses of Halides

Abstract: Introduction Functional Group Interconversion of Halides Carbon–Carbon Bond Formation Using Halides Preparation of Heterocyclic Compounds by C  Y Bond Formation Rearrangement of Halides Acknowledgements

Cited by 4 publications

References 946 publications

Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Selenium Dioxide-Mediated Bromination of α,β-Unsaturated Ketones Using N-Bromosuccinimide in the Presence of p-Toluenesulfonic Acid: A Versatile Route for the Synthesis of α′-Bromo-4-arylbut-3-en-2-one and α′,α′-Dibromo-4-arylbut-3-en-2-one

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Some Synthetic Uses of Halides

Abstract: Introduction Functional Group Interconversion of Halides Carbon–Carbon Bond Formation Using Halides Preparation of Heterocyclic Compounds by C  Y Bond Formation Rearrangement of Halides Acknowledgements

Cited by 4 publications

References 946 publications

Switching Over of the Chemoselectivity: I2-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

Switching Over of the Chemoselectivity: I2-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Selenium Dioxide-Mediated Bromination of α,β-Unsaturated Ketones Using N-Bromosuccinimide in the Presence of p-Toluenesulfonic Acid: A Versatile Route for the Synthesis of α′-Bromo-4-arylbut-3-en-2-one and α′,α′-Dibromo-4-arylbut-3-en-2-one

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Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones

Switching Over of the Chemoselectivity: I₂-DMSO-Enabled α,α-Dichlorination of Functionalized Methyl Ketones