- The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes
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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.
- Badgoti, Ranveer Singh,Dandia, Anshu,Parewa, Vijay,Rathore, Kuldeep S.,Saini, Pratibha,Sharma, Ruchi
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p. 18040 - 18049
(2021/05/29)
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- NCBSI/KI: A Reagent System for Iodination of Aromatics through in Situ Generation of I-Cl
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In situ iodine monochloride (I-Cl) generation followed by iodination of aromatics using NCBSI/KI system has been developed. The NCBSI reagent requires no activation due to longer bond length, lower bond dissociation energy, and higher absolute charge density on nitrogen. The system is adequate for mono- and diiodination of a wide range of moderate to highly activated arenes with good yield and purity. Moreover, the precursor N-(benzenesulfonyl)benzenesulfonamide can be recovered and transformed to NCBSI, making the protocol eco-friendly and cost-effective.
- Palav, Amey,Misal, Balu,Chaturbhuj, Ganesh
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p. 12467 - 12474
(2021/08/24)
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- Sulfated polyborate-H2O assisted tunable activation of N-iodosuccinimide for expeditious mono and diiodination of arenes
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Owing to both Lewis and Bronsted acid active sites on sulfated polyborate under homogenous conditions, we were keen on developing iodination protocol of arenes that can meet the requirement of regioselectivity and higher yield. The sulfated polyborate activates N-iodosuccinimide for mono iodination of highly activated substrates viz. phenols, anilines under anhydrous condition. Water tunes sulfated polyborate to generate more Bronsted acid sites resulting in rapid activation of NIS for diiodination. The protocol was equally applicable to diiodination of 4-hydroxyphenylacetic acid to synthesize 4-hydroxy-3,5-diiodophenylacetic acid, an intermediate of tiratricol, a thyroid treatment drug. This protocol was further integrated via one-pot sequential iodination and Sonogashira coupling to synthesize aryl acetylenes, building blocks for the synthesis of a variety of specialty chemicals, API, and natural products.
- Misal, Balu,Palav, Amey,Ganwir, Prerna,Chaturbhuj, Ganesh
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supporting information
(2021/05/26)
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- Selective C-H Iodination of (Hetero)arenes
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Iodoarenes are versatile intermediates and common synthetic targets in organic synthesis. Here, we present a strategy for selective C-H iodination of (hetero)arenes with a broad functional group tolerance. We demonstrate the utility and differentiation to other iodination methods of supposed sulfonyl hypoiodites for a set of carboarenes and heteroarenes.
- Tanwar, Lalita,B?rgel, Jonas,Lehmann, Johannes,Ritter, Tobias
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supporting information
p. 5024 - 5027
(2021/06/30)
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- R4NHal/NOHSO4: A Usable System for Halogenation of Isoxazoles, Pyrazoles, and beyond
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A new convenient and versatile halogenating system (R4NHal/NOHSO4), giving straightforward and general access to halogenated 3,5-diaryl- and alkylarylisoxazoles, pyrazoles and electron-rich benzenes from the corresponding scaffolds, is suggested. The method provides excellent regioselectivity, scalability to the gram scale, and a broad scope for both aromatics and halogens. A three-step, one-pot reaction protocol was developed, and a series of 3,5-diaryl-4-haloisoxazoles has been efficiently synthesized from 1,2-diarylcyclopropanes under suggested nitrosating-halogenating conditions.
- Bondarenko, Oksana B.,Karetnikov, Georgy L.,Komarov, Arseniy I.,Pavlov, Aleksandr I.,Nikolaeva, Svetlana N.
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supporting information
p. 322 - 332
(2021/01/14)
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- One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides
-
This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.
- Zupanc, An?e,Jereb, Marjan
-
p. 5991 - 6000
(2021/05/05)
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- A convenient synthetic approach to a novel class of aryldifluoromethyl pyrimidine derivatives containing strobilurin motif as insecticidal agents
-
A series of aryldifluoromethyl pyrimidine compounds containing strobilurin were synthesized through bioelectronic isometric design with azoxystrobin as the lead compound and a convenient approach to aryldifluoromethylpyrimidine intermediates was developed, which features mild reaction conditions and simple operation. The title compounds and aryldifluoromethylpyrimidine intermediates were characterized by NMR and HRMS. Both 7c and 7l of the preliminary screening tests showed 100% inhibition against Mythimna separata at 100 mg/L. At 20 mg/L, the lethal rate of 7l against Mythimna separata can be up to 80%.
- Cai, Zengfei,Cao, Yangyang,Du, Xiaohua,Hao, Shulin,Zhang, Wenliang
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supporting information
(2021/10/07)
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- Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
-
A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
- Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
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p. 12344 - 12353
(2021/09/02)
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- Aryl Diazonium Salts: Powerful Arylating Agents for Catellani-Typeortho-Arylation
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The Catellani reaction provides an efficient synthetic approach to polyfunctionalized arenes. However, the selectiveortho-arylating reagents employed in these reactions have been strictly limited to activated bromoarenes. As demonstrated in this work, aryl diazonium salts bearing both electron-donating and electron-withdrawing substituents, after in situ transformations with KI into the corresponding iodoarenes, were efficient arylating reagents for Catellani typeortho-arylation approaches.
- Fu, Ying,Guo, Liang-Liang,Zhang, Yu-Xia
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supporting information
p. 17437 - 17444
(2021/12/02)
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- Copper-Catalyzed Cycloaddition of Heterobicyclic Alkenes with Diaryl Disulfides to Synthesize Dihydrobenzo[b]thiophene Derivatives
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A novel copper-catalyzed cycloaddition of diaryl disulfides to heterobicyclic alkenes has been developed. The C - S and C - C bonds can be formed simultaneously on the C═C bond of the olefins via a single-step cycloaddition to afford a series of 2,3-dihydrobenzo[b]thiophene derivatives. This reaction exhibits excellent diastereoselectivity and relatively broad substrate scope. Various functional groups attached to the substrates are tolerated in this protocol to give the corresponding exo adducts in moderate yields.
- Lin, Qifu,Yang, Wen,Yao, Yongqi,Li, Yue,Wang, Lin,Yang, Dingqiao
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p. 4193 - 4204
(2021/03/09)
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- Preparation method of nitrogen-alkyl (deuterated alkyl) aromatic heterocycle and alkyl (deuterated alkyl) aryl ether compound
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The invention provides a method for preparing nitrogen-alkyl(deuterated alkyl)aromatic heterocycle and alkyl(deuterated alkyl)aryl ether compounds. The method adopted in the invention specifically comprises the following steps: firstly, adding an alkoxy base (MOR') or a combination reagent Q (comprising a base M'X, an alcohol C and a molecular sieve E) into a solvent B to be stirred; then, addingan aromatic compound D of nitrogen sulfonyl or oxygen sulfonyl into a mixture; separating and purifying after reaction to obtain nitrogen-alkyl(deuterated alkyl)aromatic heterocycle or alkyl(deuterated alkyl)aryl ether. The method can realize one-step conversion from an electron withdrawing benzenesulfonyl protecting group on a nitrogen or oxygen atom to an electron donating alkyl protecting group, avoids using highly toxic alkyl halide, and has advantages of being efficient, economical, environmentally friendly, mild in condition, good in substrate universality and high in yield; the prepareddeuterated compounds can be widely applied to the fields of pharmaceutical chemistry and organic chemistry synthesis.
- -
-
Paragraph 0093-0098
(2021/04/03)
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- Trialkylammonium salt degradation: Implications for methylation and cross-coupling
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Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is
- Assante, Michele,Baillie, Sharon E.,Juba, Vanessa,Leach, Andrew G.,McKinney, David,Reid, Marc,Washington, Jack B.,Yan, Chunhui
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p. 6949 - 6963
(2021/06/02)
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- Hydrocarbon-Soluble Halogen and Thiolate/Magnesium Exchange Reagents
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The invention relates to hydrocarbon-soluble halogen or thiolate/magnesium exchange reagents of the general formula [in-line-formulae]R1MgR11?n(OR3)n·LiOR2·(1?n)LiOR3·aDonor[/in-line-formulae] in which: R1 is a C1-C8 alkyl and OR2 as well as OR3 are same or different and represent primary, secondary, or tertiary alkoxide residues having 3 to 18 carbon atoms, wherein R2 and/or R3 can for their part contain an alkoxy substituent OR4; a assumes a value of 0 to 2, n assumes a value between 0 and 1, and the donor is an organic molecule containing at least 2 nitrogen atoms.
- -
-
Paragraph 0071; 0096-0101
(2020/08/19)
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- Protecting Group-Controlled Remote Regioselective Electrophilic Aromatic Halogenation Reactions
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Being able to utilize a protecting group to influence remote regiocontrol offers a simple alternative approach to direct late-stage functionalization of complex organic molecules. However, protecting groups that have the ability to influence reaction regi
- Brittain, William D. G.,Cobb, Steven L.
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p. 6862 - 6871
(2020/07/07)
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- Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
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The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
- Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
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p. 176 - 180
(2019/12/11)
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- Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust
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Readily available aryldimethylsulfonium triflates react with zinc powder under nickel catalysis via the selective cleavage of the sp2-hybridized carbon-sulfur bond to produce salt-free arylzinc triflates under mild conditions. This zincation displays superb chemoselectivity and thus represents a protocol that is complementary or orthogonal to existing methods. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.
- Yamada, Kodai,Yanagi, Tomoyuki,Yorimitsu, Hideki
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p. 9712 - 9718
(2021/01/09)
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- Fluorinations of unsymmetrical diaryliodonium salts containing: Ortho -sidearms; Influence of sidearm on selectivity
-
Activated aromatics were reacted with two different fluoroidoane reagents 1 and 2 in the presence of triflic acid to prepare only the para-substituted diaryliodonium salts. With fluoroiodane 1 the unsymmetrical diaryliodonium salts contained an ortho-propan-2-ol sidearm, whereas the alcohol sidearm was eliminated to form an ortho-styrene sidearm in the reaction with fluoroiodane 2. Only the diaryliodonium salts containing a styrene sidearm were fluorinated successfully to deliver para-fluorinated aromatics in good yields.
- Abudken, Ahmed M. H.,Hope, Eric G.,Singh, Kuldip,Stuart, Alison M.
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p. 6140 - 6146
(2020/10/30)
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- Orthogonal Stability and Reactivity of Aryl Germanes Enables Rapid and Selective (Multi)Halogenations
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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.
- Deckers, Kristina,Fricke, Christoph,Schoenebeck, Franziska
-
supporting information
p. 18717 - 18722
(2020/08/25)
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- Arene diazonium saccharin intermediates: A greener and cost-effective alternative method for the preparation of aryl iodide
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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.
- Ghaffari Khaligh, Nader,Rafie Johan, Mohd,Shahnavaz, Zohreh,Zaharani, Lia
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p. 535 - 542
(2020/06/01)
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- Photochemical Transformation of O-(β-Arylethyl) Arylimidates into 2,4-Diaryl-5-iodoxazoles with 1,3-Diiodo-5,5-dimethylhydantoin
-
Treatment of O-(β-arylethyl) arylimidates with 1,3-diiodo-5,5-dimethylhydantoin (DIH) under irradiation with a tungsten lamp in 1,2-dichloroethane gave the corresponding 2,4-diaryl-5-iodoxazoles and 2,4-diaryloxazoles in good to moderate yields, respectively, depending on the aryl group. It was proposed that the reactions proceeded through the formation of N-iodoimidates by the reaction of O-(β-arylethyl) arylimidates with DIH, followed by the formation of iminyl radicals via homolytic N–I bond cleavage, the 1,5-H shift by the iminyl radicals, the C–I bond formation of the formed carbon-centered radicals with iodine, the nucleophilic cyclization by the imino groups to form 2,4-diaryloxazolines, the oxidation of the formed 2,4-diaryloxazolines to 2,4-diaryloxazoles, and the iodination of the formed 2,4-diaryloxazoles to 2,4-diaryl-5-iodoxazoles with DIH.
- Saito, Aya,Togo, Hideo
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p. 3320 - 3331
(2020/06/01)
-
- Mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen: Development of a base-catalyzed iododeboronation for radiolabeling applications
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An investigation into the mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen reagents is reported. Evidence is provided to show that this takes place via a boronate-driven ipso-substitution pathway and that Cu is not required for these processes to operate: General Lewis base catalysis is operational. This in turn allows the rational development of a general, simple, and effective base-catalyzed halodeboronation that is amenable to the preparation of 125I-labeled products for SPECT applications.
- Molloy, John J.,O'rourke, Kerry M.,Frias, Carolina P.,Sloan, Nikki L.,West, Matthew J.,Pimlott, Sally L.,Sutherland, Andrew,Watson, Allan J. B.
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supporting information
p. 2488 - 2492
(2019/04/10)
-
- ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents
-
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.
- Fu, Fang,Gurung, Laxman,Czaun, Miklos,Mathew, Thomas,Prakash, G.K. Surya
-
supporting information
(2019/08/26)
-
- Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
-
A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
- Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
-
supporting information
p. 6445 - 6448
(2019/06/07)
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- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
-
-
- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
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p. 7411 - 7417
(2019/06/18)
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- Photocatalytic Oxidative Iodination of Electron-Rich Arenes
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A visible-light-mediated oxidative iodination of electron-rich arenes has been developed. 2.5 mol% of unsubstituted anthraquinone as photocatalyst were used in combination with elementary iodine, trifluoroacetic acid and oxygen as the terminal oxidant. The iodination proceeds upon irradiation in non- or weakly-electron donating solvents (DCM, DCE and benzene) wherein a spectral window in strongly coloured iodine solutions can be observed at around 400 nm. The method provides good to excellent yields (up to 98%) and shows excellent regioselectivity and good functional group tolerance (triple bonds, ketone, ester, amide). Moreover, the photo-iodination was also upscaled to a 5 mmol scale (1.1 g). Mechanistic investigations by intermediate trapping and competition experiments indicate a photocatalytic arene oxidation and the subsequent reaction with iodine as a likely mechanistic pathway. (Figure presented.).
- Narobe, Rok,Düsel, Simon J. S.,Iskra, Jernej,K?nig, Burkhard
-
supporting information
p. 3998 - 4004
(2019/07/17)
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- One-pot synthesis of unsymmetrical 1,3-butadiyne derivatives and their application in the synthesis of unsymmetrical 2,5-diarylthiophenes
-
A one-pot protocol was developed for the synthesis of unsymmetrical 1,3-butadiynes. The procedure is based on two sequential reactions: deprotection of R–C≡C–C≡C– C(Me)2OH derivatives in a retro-Favorskii reaction to furnish a terminal 1,3-butadiyne compound, which reacted with aryl iod-ides in a Sonogashira-type cross-coupling reaction catalyzed by Pd(PPh3)4 and CuI, using TBAOH as activator and toluene as solvent under reflux for 10 min. We also studied in situ thiocycli-zation of 1,3-butadiynes, leading to unsymmetrical 2,5-diaryl-thiophenes. The principal features of this method are operational simplicity, good substrate scope, very fast reaction, and high yields.
- Andrade, Camila B.,Carvalho, Diego B.,Trefzger, Ozildéia S.,Kassab, Najla M.,Guerrero, Palimécio G.,Barbosa, Sandro L.,Shiguemoto, Cristiane Y. K.,Baroni, Adriano C. M.
-
supporting information
p. 696 - 704
(2019/01/04)
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- Method for catalyzing deaminized boric acid esterification or halogenation of arylamine
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The invention belongs to the technical field of organic synthesis and in particular discloses a method for catalyzing deaminized boric acid esterification or halogenation of arylamine. The method comprises the following steps: putting arylamine and a nitroso type compound into a mixed solvent, and performing a reaction at 0-5 DEG; and further adding a raw material capable of providing a functionalization group A and a catalysis amount of a reaction accelerator, and performing deamination functionalization reaction under light radiation at 10-50 DEG C, so as to obtain a product that an amino site of the arylamine is modified by the functionalization group A. Due to synergetic control on substrates, reaction solvents, material mixing modes, temperatures, reaction accelerators and addition amounts, boric acid esterification or halogenation of arylamine, particularly electron donating substituted arylamine which is hard to treat effectively in technical schemes of the industry, can be achieved.
- -
-
Paragraph 0063; 0088-0090
(2020/01/12)
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- Synthesis, structure, and synthetic potential of arenediazonium trifluoromethanesulfonates as stable and safe diazonium salts
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Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+ TfO– can be obtained easily and in high yields by diazotization of anilines with tert-butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf-stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal-free chlorodediazonization reaction with chloroform and CCl4.
- Filimonov, Victor D.,Krasnokutskaya, Elena A.,Kassanova, Assia Zh.,Fedorova, Valentina A.,Stankevich, Ksenia S.,Naumov, Nikolay G.,Bondarev, Alexander A.,Kataeva, Veronika A.
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p. 665 - 674
(2018/09/14)
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- One of iodinated aromatic ring by iodine chloride in hydrochloric acid (by machine translation)
-
[Problem] to one iodine chloride is used, and, stably iodinated aromatic compound can be iodinated aromatic compound production. [Solution] water containing one iodine chloride hydrogen chloride, iodine chloride content of 30% by mass of the first mass % -70, 3 mass % -20 mass % aqueous solution of hydrogen chloride content in the preparing step, a process for preparing an aromatic compound as the reaction substrate, the reaction substrate as an aqueous solution of the mixture of aromatic compounds, as the reaction substrate of one iodine chloride by reacting an aromatic compound, iodinated aromatic compound obtained in the step, the iodinated aromatic compound. [Drawing] no (by machine translation)
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Paragraph 0063-0066
(2019/09/10)
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- Facile Access to Diverse Libraries of Internal Alkynes via Sequential Iododediazoniation/Decarboxylative Sonogashira Reaction in Imidazolium ILs without Ligand or Additive
-
Convenient access to diverse libraries of internal alkynes via decarboxylative Sonogashira reaction of alkynyl-carboxylic acids with iodoarenes, employing imidazolium-ILs as solvent, along with piperidine-appended imidazolium [PAIM][NTf2] as task-specific basic IL is demonstrated, without the need for any ligand or additive. The feasibility to perform these reactions by sequential one-pot iododediazoniation/decarboxylative Sonogashira reaction is also shown, and the scope of the methods is underscored by providing 29 examples. The potential for recycling and reuse of the IL solvent is also examined.
- Prabhala, Pavankumar,Savanur, Hemantkumar M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
p. 2061 - 2064
(2019/03/07)
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- Detosylative (Deutero)alkylation of Indoles and Phenols with (Deutero)alkoxides
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An efficient strategy for N/O-(deutero)alkylation of indoles and phenols with alkoxides/alcohols as the alkylation reagents is described. The consecutive detosylation/alkylation transformations feature mild reaction conditions, high ipso-selectivity, and good functional group tolerance (>50 examples). A one-pot selective N-alkylation of unprotected indoles with alcohols and TsCl is also realized. The application of this method is demonstrated by the introduction of isotope-labeled (CD3 and 13CH3) groups using the readily accessible labeled alcohols and the synthesis of pharmaceuticals.
- Zhu, Ming-Hui,Yu, Cheng-Long,Feng, Ya-Lan,Usman, Muhammad,Zhong, Dayou,Wang, Xin,Nesnas, Nasri,Liu, Wen-Bo
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supporting information
p. 7073 - 7077
(2019/09/30)
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- Rapid Iododeboronation with and without Gold Catalysis: Application to Radiolabelling of Arenes
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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.
- Webster, Stacey,O'Rourke, Kerry M.,Fletcher, Conor,Pimlott, Sally L.,Sutherland, Andrew,Lee, Ai-Lan
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supporting information
p. 937 - 943
(2017/12/26)
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- Visible-Light-Induced Decarboxylative Iodination of Aromatic Carboxylic Acids
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A convenient, efficient and practical visible-light-induced decarboxylative iodination of aromatic carboxylic acids has been developed, and the corresponding aryl iodides were obtained in good yields. The method shows some advantages including the use of readily available aromatic carboxylic acids as the starting materials, simple and mild conditions, high efficiency, wide substrate scope and tolerance of various functional groups.
- Jiang, Min,Yang, Haijun,Jin, Yunhe,Ou, Lunyu,Fu, Hua
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supporting information
p. 1572 - 1577
(2018/06/26)
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- Electrochemical Synthesis of Aryl Iodides by Anodic Iododesilylation
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An electrochemical access to iodinated aromatic compounds starting from trimethylsilyl-substituted arenes is presented. By design of experiments, highly efficient and mild conditions were identified for a wide range of substrates. A functional group stability test and the synthesis of an important 3-iodobenzylguanidine radiotracer illustrate the scope of this process.
- M?ckel, Robert,Hille, Jessica,Winterling, Erik,Weidemüller, Stephan,Faber, Tabea Melanie,Hilt, Gerhard
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supporting information
p. 442 - 445
(2018/02/21)
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- Generation of Aryl and Heteroaryl Magnesium Reagents in Toluene by Br/Mg or Cl/Mg Exchange
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The alkylmagnesium alkoxide sBuMgOR?LiOR (R=2-ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR?LiOR) in toluene. These Grignard reagents react with a broad range of electrophiles, including aldehydes, ketones, allyl bromides, acyl chlorides, epoxides, and aziridines, in good yields. Remarkably, the related reagent sBu2Mg?2 LiOR (R=2-ethylhexyl) undergoes Cl/Mg exchange with various electron-rich aryl chlorides in toluene, producing diorganomagnesium species of type Ar2Mg?2 LiOR, which react well with aldehydes and allyl bromides.
- Ziegler, Dorothée S.,Karaghiosoff, Konstantin,Knochel, Paul
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supporting information
p. 6701 - 6704
(2018/05/05)
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- Synthetic method of 4-iodoanisole
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The invention relates to the technical field of synthesis of drug intermediates and particularly relates to a synthetic method of 4-iodoanisole. The synthetic method comprises the following steps: with phenyl ether as a substrate, simultaneously dropwise
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Paragraph 0015; 0021-0035
(2018/09/11)
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- Metal-Free, Oxidant-Free, and Controllable Graphene Oxide Catalyzed Direct Iodination of Arenes and Ketones
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A direct, metal-free, and oxidant-free method for the graphene oxide (GO)-catalyzed iodination of arenes and ketones with iodine in a neutral medium was explored. This iodination protocol was performed by using a simple technique to avoid the use of external metal catalysts and oxidants and harsh acidic/basic reaction conditions. In addition, by this method the degree of iodination could be controlled, and the reaction was scalable and compatible with air. This strategy opens a new field for GO-catalyzed chemistry and provides an avenue for the convenient direct iodination of arenes and ketones.
- Zhang, Jingyu,Li, Shiguang,Deng, Guo-Jun,Gong, Hang
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p. 376 - 380
(2017/12/07)
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- A simple and efficient iodination of aromatic compounds using I2/Choline Chloride/K2S2O8
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A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of molecular iodine, choline chloride and potassium peroxodisulfate at 65 °C in acetonitrile. The rate of conversion of aromatic compounds into iodoaromatic compounds was promoted by in situ formed choline peroxodisulfate. This protocol provides an efficient access to iodoarenes with operational simplicity, good functional group tolerance and a moderate to good product yield.
- Parthiban,Joel Karunakaran
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p. 1659 - 1663
(2018/06/12)
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- Palladium-Catalyzed β-Arylation of Amide via Primary sp3C-H Activation
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A β-arylation of primary sp3C-H bonds on simple amides such as pivalamides with aryl iodides/CF3CO2Ag has been established successfully at 120 °C in a Pd(OAc)2 (catalyst)/CF3CH2OH (solvent) system. Pivalamides including tBuCONH2, tBuCONHR, and tBuCONR2 undergo the arylations smoothly to afford β-aryl pivalamides in moderate to good yields. Various aryl iodides are available bearing either electron-donating or electron-withdrawing substituted groups in the coupling reactions.
- Zhao, Ren,Lu, Wenjun
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supporting information
p. 2188 - 2192
(2018/07/25)
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- Perovskite hole transport material based on triptycene mother nucleus and preparation method thereof
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The present invention discloses a perovskite hole transport material based on a triptycene mother nucleus and a preparation method thereof. The material is 2,6,14-tri(50-(N,N-bi(4-methoxyphenyl)aminophenol-4-yl)-3,4-ethylenedioxythiophene-2-yl)-triptycene. The preparation method has the advantages of mild synthesis conditions, simple steps, cheap and easily obtained synthetic raw materials, and low synthesis costs. The prepared material has a good thermal stability, solubility and film forming property. An ultraviolet-visible light absorption spectrum indicates the hole transport material based on the triptycene mother nucleus has a large conjugate structure, has a more suitable HOMO level (-5.08 eV) than that of a mainstream hole transport material Spiro-MeOTAD, and provides a strong driving force for hole transporting. The carrier mobility of the material measured by a space charge limiting current method is 8x10cm.Vs. The perovskite hole transport material has potential.
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Paragraph 0061-0064
(2018/11/03)
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- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
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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.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
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supporting information
p. 14622 - 14626
(2018/09/21)
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- Direct Pd(II)-Catalyzed Site-Selective C5-Arylation of 2-Pyridone Using Aryl Iodides
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A straightforward Pd(II)-catalyzed general strategy was developed for the C5-selective arylation of the 2-pyridone core with easily available aryl iodides. The transformation was highly regioselective and accomplished with a wide scope and functional group tolerance. Silver nitrate played a crucial role in this direct site-selective arylation. The method was extended to synthesize biologically active molecules.
- Maity, Saurabh,Das, Debapratim,Sarkar, Souradip,Samanta, Rajarshi
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supporting information
p. 5167 - 5171
(2018/09/13)
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- Effect of alkyl chain length on the properties of triphenylamine-based hole transport materials and their performance in perovskite solar cells
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A new series of diacetylide-triphenylamine (DATPA) derivatives with five different alkyl chains in the para position, MeO, EtO, nPrO, iPrO and BuO, were synthesised, fully characterised and their function as hole-transport materials in perovskite solar cells (PSC) studied. Their thermal, optical and electrochemical properties were investigated along with their molecular packing and charge transport properties to analyse the influence of different alkyl chains in the solar cell parameters. The shorter alkyl chain facilitates more compact packing structures which enhanced the hole mobilities and reduced recombination. This work suggests that the molecule with the methoxy substituent (MeO) exhibits the best semiconductive properties with a power conversion efficiency of up to 5.63%, an open circuit voltage (Voc) of 0.83 V, a photocurrent density (Jsc) of 10.84 mA cm-2 and a fill factor of 62.3% in perovskite solar cells. Upon replacing the methoxy group with longer alkyl chain substituents without changing the energy levels, there is a decrease in the charge mobility as well as PCE (e.g. 3.29% for BuO-DATPA). The alkyl chain length of semiconductive molecules plays an important role in achieving high performance perovskite solar cells.
- Fuentes Pineda, Rosinda,Troughton, Joel,Planells, Miquel,Sanchez-Molina Santos, Irene,Muhith, Farmin,Nichol, Gary S.,Haque, Saif,Watson, Trystan,Robertson, Neil
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p. 1252 - 1260
(2018/01/17)
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- Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol
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Regioselective halogenation of arenes and heterocycles with N-halosuccinimides in fluorinated alcohols is disclosed. Under mild condition reactions, a wide diversity of halogenated arenes are obtained in good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of one-pot sequential halogenation and halogenation-Suzuki cross-coupling reactions.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
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p. 930 - 938
(2018/01/28)
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- An efficient gram scale synthesis of aryl iodides from aryl diazofluoroborates in water under mild conditions
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Transition metal-free synthesis of synthetically valuable aryl iodides from aryl diazofluroborates in water under mild conditions has been described. Majority of synthesized aryl iodides are obtained in quantitative yields (>99%) under present reaction conditions. The structural effects due to the substituents present on aryl diazofluoroborates did not show any satisfactory effect on the yields of the aryl iodides. Hence, the methodology presented here was found to be adventitious for the quantitative production of synthetically valuable aryl iodides.
- Gholap, Somnath S.
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p. 594 - 599
(2018/06/26)
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- A general electrochemical strategy for the Sandmeyer reaction
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Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
- Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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p. 8731 - 8737
(2018/12/10)
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- Ketyl radical reactivity via atom transfer catalysis
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Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms.We report a strategy for net redox-neutral generation and reaction of ketyl radicals.The in situ conversion of aldehydes to a-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z-selectivity.
- Wang, Lu,Lear, Jeremy M.,Rafferty, Sean M.,Fosu, Stacy C.,Nagib, David A.
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p. 225 - 229
(2018/11/27)
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- Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
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Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
- Lee, Yong Ho,Morandi, Bill
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p. 1016 - 1022
(2018/09/06)
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- Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
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We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
- De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
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supporting information
p. 10140 - 10144
(2018/08/23)
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