Nickel-catalysed aromatic Finkelstein reaction of aryl and heteroaryl bromides

Cant, Alastair A.; Bhalla, Rajiv; Pimlott, Sally L.; Sutherland, Andrew

doi:10.1039/c2cc30956d

Cited by 63 publications

(32 citation statements)

References 18 publications

(9 reference statements)

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“…XXXX, XXX, XXX−XXX -poor aromatics (Scheme 163). 297 The reaction was found to proceed well with NiBr 2 and PBu 3 in NMP as solvent, however, high temperatures (140−190°C) were needed to get synthetically useful yields of the aryl iodide products. The reaction times could be dramatically reduced by the use of microwave irradiation, 298 This efficient stoichiometric reaction is extremely rapid and reaches completion in less than 1 min in MeCN.…”

Section: Ni-catalyzed Synthesis Of Aryl Halidesmentioning

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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Section: Ni-catalyzed Synthesis Of Aryl Halidesmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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“…3, 133.7, 133.6, 132.5, 130.6, 127.7, 119.9. 18 Following the typical procedure gave 2i as a white solid; yield: 104 mg (84%); mp 178.1-179.0 °C. 13 C NMR (100 MHz, DMSO-d 6 ): δ = 165.…”

Section: -Fluorobenzoic Acid (2f) 2hmentioning

confidence: 99%

Ligand-Free Palladium-Catalyzed Hydroxycarbonylation of Aryl Halides under Ambient Conditions: Synthesis of Aromatic Carboxylic Acids and Aromatic Esters

2015

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“…A few recently developed copper-or nickel-catalyzed strategies for aryl iodide preparation have been established in which aryl chlorides and bromides react with inorganic iodides such as NaI or KI (Fig. 2a) [12][13][14][15] . However, each of these methods has limited substrate scope and has other limitations, which include a requirement for high temperatures ( > 100 °C), transition metals (Cu or Ni) and/or specially designed ligands such as diamine and phosphine ligands.…”

Section: Introductionmentioning

confidence: 99%

Photo-induced iodination of aryl halides under very mild conditions

Liu

et al. 2016

Nat Protoc

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Aryl iodides are important precursors in synthetic chemistry that form carbon–carbon and carbon–heteroatom bonds. Most methods use transition-metal catalysts, which need to be scrupulously removed before the compounds can be used in the pharmaceutical and electronics industries, where only parts-per-million levels of transition metals are allowed. The aromatic Finkelstein iodination reaction is a powerful method of preparing valuable aryl iodides from cheap but less reactive aryl bromides and chlorides. This protocol describes a transition metal–free method for a photo-induced aromatic Finkelstein iodination reaction that is performed at room temperature (20 °C). With common aromatic bromides and sodium iodide (NaI) as the starting materials, as well as a catalytic amount of I2 as an additive, the corresponding aromatic iodides can be synthesized in yields ranging from 56 to 93% under UV light irradiation in the absence of any metal catalysts. Various functional groups such as nitrile, ester and amino can be tolerated, which will facilitate the further functionalization of the aromatic iodides. The procedure normally requires 38–40 h to complete

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Nickel-catalysed aromatic Finkelstein reaction of aryl and heteroaryl bromides

Cited by 63 publications

References 18 publications

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Ligand-Free Palladium-Catalyzed Hydroxycarbonylation of Aryl Halides under Ambient Conditions: Synthesis of Aromatic Carboxylic Acids and Aromatic Esters

Photo-induced iodination of aryl halides under very mild conditions

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