589-87-7Relevant academic research and scientific papers
Acidic ionic liquid supported on silica-coated magnetite nanoparticles as a green catalyst for one-pot diazotization-halogenation of the aromatic amines
Isaad, Jalal
, p. 49333 - 49341 (2014)
Acidic ionic liquid was immobilized on silica-coated magnetite nanoparticles (Fe3O4@SILnP) and used as an efficient heterogeneous catalyst for the diazotization-iodination reaction of different aromatic amines under solvent-free conditions at room temperature. The diazonium salts that are formed by this catalyst are stable at room temperature and react rapidly with sodium iodide to produce aryl iodides in good to excellent yields. This method has some advantages such as low pollution, rapid access to products, simple work-up and easy separation of catalyst from the reaction mixture.
The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
, p. 18040 - 18049 (2021/05/29)
An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.
Hydrogen-Bond-Donor Solvents Enable Catalyst-Free (Radio)-Halogenation and Deuteration of Organoborons
Yang, Yi,Gao, Xinyan,Zeng, Xiaojun,Han, Junbin,Xu, Bo
supporting information, p. 1297 - 1300 (2020/12/23)
A hydrogen bond donor solvent assisted (radio)halogenation and deuteration of organoborons has been developed. The reactions exhibited high functional group tolerance and needed only an ambient atmosphere. Most importantly, compared to literature methods, our conditions are more consistent with the principals of green chemistry (e.g., metal-free, strong oxidant-free, more straightforward conditions).
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
Arene diazonium saccharin intermediates: A greener and cost-effective alternative method for the preparation of aryl iodide
Ghaffari Khaligh, Nader,Rafie Johan, Mohd,Shahnavaz, Zohreh,Zaharani, Lia
, p. 535 - 542 (2020/06/01)
In the current protocol, the arene diazonium saccharin derivatives were initially produced from various substituted aromatic amines; subsequently, these intermediates were treated with a greener organic iodide for the preparation of the aryl iodide. We tried to choose low-cost, commercially available, biodegradable, recoverable, ecofriendly, and safe reagents and solvents. The arene diazonium saccharin intermediates could be stored in the liquid phase into a refrigerator for a long time with no significant loss activity. The outstanding merits of the current protocol (a) included the partial recovering of saccharin and tetraethylammonium salt, (b) reduce the use of solvents and the reaction steps due to eliminating separation and purification of intermediates, (c) good yield of the sterically hindered substrates, and (d) avoid the generation of heavy metal or corrosive waste.
Orthogonal Stability and Reactivity of Aryl Germanes Enables Rapid and Selective (Multi)Halogenations
Deckers, Kristina,Fricke, Christoph,Schoenebeck, Franziska
supporting information, p. 18717 - 18722 (2020/08/25)
While halogenation is of key importance in synthesis and radioimaging, the currently available repertoire is largely designed to introduce a single halogen per molecule. This report makes the selective introduction of several different halogens accessible. Showcased here is the privileged stability of nontoxic aryl germanes under harsh fluorination conditions (that allow selective fluorination in their presence), while displaying superior reactivity and functional-group tolerance in electrophilic iodinations and brominations, outcompeting silanes or boronic esters under rapid and additive-free conditions. Mechanistic experiments and computational studies suggest a concerted electrophilic aromatic substitution as the underlying mechanism.
ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents
Fu, Fang,Gurung, Laxman,Czaun, Miklos,Mathew, Thomas,Prakash, G.K. Surya
supporting information, (2019/08/26)
Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids. These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products with high selectivity and yields.
Zinc-Catalysed Hydroboration of Terminal and Internal Alkynes
Mandal, Souvik,Mandal, Sayantan,Geetharani
supporting information, p. 4553 - 4556 (2019/08/20)
A regioselective hydroboration of alkynes has been developed by using commercially available zinc triflate as a catalyst, in the presence of catalytic amount of NaBHEt3. The reaction tolerates a wide range of terminal alkynes having several synthetically useful functional groups and proceeds regioselectively to furnish hydroborated products in moderate to excellent yields. This system shows moderate chemoselectivity towards terminal C≡C bond over terminal and internal C=C bond and internal C≡C bond.
Rapid Iododeboronation with and without Gold Catalysis: Application to Radiolabelling of Arenes
Webster, Stacey,O'Rourke, Kerry M.,Fletcher, Conor,Pimlott, Sally L.,Sutherland, Andrew,Lee, Ai-Lan
supporting information, p. 937 - 943 (2017/12/26)
Radiopharmaceuticals that incorporate radioactive iodine in combination with single-photon emission computed tomography imaging play a key role in nuclear medicine, with applications in drug development and disease diagnosis. Despite this importance, there are relatively few general methods for the incorporation of radioiodine into small molecules. This work reports a rapid air- and moisture-stable ipso-iododeboronation procedure that uses NIS in the non-toxic, green solvent dimethyl carbonate. The fast reaction and mild conditions of the gold-catalysed method led to the development of a highly efficient process for the radiolabelling of arenes, which constitutes the first example of an application of homogenous gold catalysis to selective radiosynthesis. This was exemplified by the efficient synthesis of radiolabelled meta-[125I]iodobenzylguanidine, a radiopharmaceutical that is used for the imaging and therapy of human norepinephrine transporter-expressing tumours.
Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
Mukhopadhyay, Sushobhan,Batra, Sanjay
supporting information, p. 14622 - 14626 (2018/09/21)
A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
