High-yielding one-pot synthesis of diaryliodonium triflates from arenes and iodine or aryl iodides

Unsymmetric and symmetric diaryliodonium triflates are synthesized from both electron-deficient and electron-rich substrates in a fast, high yielding, and operationally simple protocol employing arenes and aryl iodides or iodine.     

Regiospecific one-pot synthesis of diaryliodonium tetrafluoroborates from arylboronic acids and aryl iodides

Diaryliodonium salts have recently received considerable attention as mild arylation reagents in organic synthesis. This paper describes a regiospecific, sequential one-pot synthesis of symmetrical and unsymmetrical diaryliodonium tetrafluoroborates, which are the most popular salts in metal-catalyzed arylations. The protocol is fast and high-yielding and has a large substrate scope. Furthermore, the corresponding diaryliodonium triflates can conveniently be obtained via an in situ anion exchange.     

Copper-catalyzed synthesis of 2-sulfenylindoles from indoline-2-thiones and aryl iodides

A novel and efficient method for synthesis of 2-sulfenylindole via copper-catalyzed coupling reaction of indoline-2-thiones with aryl iodides has been developed. A series of N-substituted and N-free 2-sulfenylindole were obtained in high yields. Furthermore, the method was employed to synthesis of benzothieno[2,3-b]indoles from indoline-2-thiones with 1,2-diiodobenzene in the presence of CuI and Pd(OAc)₂ as catalysts.     

Sequential unsymmetrical aryl coupling of o-substituted aryl iodides with o-bromophenols and reaction with olefins: palladium-catalyzed synthesis of 6H-dibenzopyran derivatives

Dibenzopyran derivatives are prepared by palladium- and norbornene-catalyzed reaction of aryl iodides, o-substituted with electron-releasing substituents, o-bromophenols, and activated alkenes.     

A facile synthesis of aryl iodides via potassium aryltrifluoroborates

Aryl- and heteroaryltrifluoroborates are rapidly converted to aryl and heteroaryl iodides under mild conditions using sodium iodide in the presence of mild oxidizing agents.     

Rhodium-catalyzed triarylphosphine synthesis via cross-coupling of aryl iodides and acylphosphines

Rhodium(I)-catalyzed C–P cross-coupling reaction with aryl iodides and acylphosphines was disclosed for a straight forward synthesis of triarylphosphines. The acylphosphines were successfully employed as both the phosphorus source and the ligand to the Rh(I) catalyst. The triarylphosphines could be afforded in a yield up to 98% with good toleration of wide functional groups.     

Palladium-catalyzed carbonylative synthesis of N-cyanobenzamides from aryl iodides/bromides and cyanamide

A novel and convenient protocol for the synthesis of N-cyanobenzamides starting from readily available aryl halides and cyanamide via palladium-catalyzed aminocarbonylation has been developed. The protocol utilizes Mo(CO)₆ as the CO source or CO(gas) and affords the desired N-cyanobenzamides in moderate to good yields.     

Copper-catalyzed direct preparation of diaryl sulfides from aryl iodides using potassium thiocyanate as a sulfur transfer reagent

A method for direct preparation of diaryl sulfides from aryl iodides using potassium thiocyanate as a sulfur-transfer agent is reported. A catalyst system comprising of a simple copper salt, tetrabutylammonium bromide as a phase-transfer agent and water as the solvent is used. Microwave heating at 200 °C for 60 min allows for the conversion of a range of aryl iodides to the corresponding diaryl sulfides.     

An efficient palladium-catalyzed synthesis of cinnamaldehydes from acrolein diethyl acetal and aryl iodides and bromides

The reaction of aryl iodides and bromides with acrolein diethyl acetal in the presence of Pd(OAc)(2), (n)()Bu(4)NOAc, K(2)CO(3), KCl, and DMF, at 90 degrees C until the disappearance of the acetal followed by the addition of 2 N HCl to the crude reaction mixture, affords cinnamaldehydes in good to high yields. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, dialkylamino, nitrile, and nitro groups. The presence of substituents close to the oxidative addition site does not hamper the reaction.     

Carbonylative cross-coupling of ortho-disubstituted aryl iodides. convenient synthesis of sterically hindered aryl ketones

A mild and general protocol for the carbonylative cross-coupling of sterically hindered ortho-disubstituted aryl iodides is reported. Carbonylative Suzuki-Miyaura couplings of a variety of aryl boronic acids provide an array of substituted biaryl ketones in modest to excellent yield. A carbonylative Negishi coupling that utilizes alkynyl nucleophiles is also described.     

Facile synthesis of S-arylisothioureas via the S-arylation of arylthioureas with aryl iodides in water

An environmentally benign, simple and highly efficient protocol for the synthesis of S-arylisothiourea derivatives has been achieved in good to excellent yields by reacting a series of aryl iodides with arylthioureas, using inexpensive CuSO₄·5H₂O as catalyst in water without PTC (phase transfer catalyst). The protocol features easy performance, good to excellent yields, good tolerance towards a variety of functional groups, which could be useful for the preparation of some biologically active compounds.     

A novel and direct synthesis of chroman derivatives using a hypervalent iodine(III) reagent

The direct aromatic carbon-oxygen bond-formation reaction was described and the novel and simple synthetic method for chroman derivatives involving aromatic cation radical intermediates was developed using the hypervalent iodine(III) reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA).     

Facile synthesis of phenacyl iodides from styrenes under visible light irradiation with fluorescent lamps

Phenacyl iodides were easily synthesized from styrenes with iodine under irradiation of visible light from a fluorescent lamp.     

Facile one-pot synthesis of novel highly functionalized dihydro-1H-pyrrole derivatives catalyzed by molecular iodine

An efficient, environmentally benign and molecular iodine promoted protocol was described for cascade synthesis of two kinds of novel dihydro-1H-pyrrole derivatives, 5 and 7. Compounds 5 were prepared via four-component reaction between diethyl acetylenedicarboxylate (DEAD), aromatic amines and phenylglyoxal monohydrate catalyzed by 10 mol% of iodine in ethanol at room temperature. In addition, using same reaction conditions, a three-component reaction between (E)-N-methyl-1-(methylthio)-2-nitroethenamine (NMSM), aromatic amines and arylglyoxal monohydrate was performed to access product 7. These transformations apparently proceed through an imine intermediate followed by iodine induced Mannich reaction and subsequent intra-molecular cyclization sequences. The protocol involves the formation of CN, CC and OH bonds leading to the preparation of a hexa substituted five membered ring with two stereo centres. The syntheses avoid the use of traditional column chromatography and recrystallization purification methods and, hence, follow the group-assisted purification (GAP) chemistry process.     

Facile synthesis of acyl sulfonamides from carboxyic acids using the Mukaiyama reagent

A fast and convenient method using the Mukaiyama reagent was developed to prepare acyl sulfonamides from carboxylic acids and sulfonamides. This methodology is effective for a range of acids and sulfonamides proceeding in moderate to good yields with the majority of reactions complete within one hour under the optimized condition.     

Copper-mediated fluorination of aryl iodides

The synthesis of aryl fluorides has been studied intensively because of the importance of aryl fluorides in pharmaceuticals, agrochemicals, and materials. The stability, reactivity, and biological properties of aryl fluorides can be distinct from those of the corresponding arenes. Methods for the synthesis of aryl fluorides, however, are limited. We report the conversion of a diverse set of aryl iodides to the corresponding aryl fluorides. This reaction occurs with a cationic copper reagent and silver fluoride. Preliminary results suggest this reaction is enabled by a facile reductive elimination from a cationic arylcopper(III) fluoride.