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Copper(I)-catalyzed N-arylation (both N1- and N3-) of hydantoins with diaryliodonium salts as aryl partners at room temperature is reported. The transformation allows diverse scopes on both hydantoins and diaryliodonium salts deliver

A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.

We have developed a simple and effective method for the C-3 arylation of phosphorus-containing indole compounds in the presence of CuI under mild conditions. This reaction provides a reliable method for the modification of ligands.

The first example of a directed and regioselective arylation of polycyclic aromatic hydrocarbons (PAHs) by using a PO directing group is reported herein. The protocol uses a cheap copper catalyst, and results in a breakthrough meta-selective C-H functionalization of arylphosphine oxide compounds. Substrates with potential fluorescence properties, for example, pyrene and fluoranthene, were successfully arylated under the system, thus achieving an efficient modification of fluorescent molecules containing the PO functional group. This journal is

Equilibrium constants for the associations of 17 diaryliodonium salts Ar2I+X- with 11 different Lewis bases (halide ions, carboxylates, p-nitrophenolate, amines, and tris(p-anisyl)phosphine) have been investigated by titrations followed by photometric or conductometric methods as well as by isothermal titration calorimetry (ITC) in acetonitrile at 20 °C. The resulting set of equilibrium constants KI covers 6 orders of magnitude and can be expressed by the linear free-energy relationship lg KI = sI LAI + LBI, which characterizes iodonium ions by the Lewis acidity parameter LAI, as well as the iodonium-specific affinities of Lewis bases by the Lewis basicity parameter LBI and the susceptibility sI. Least squares minimization with the definition LAI = 0 for Ph2I+ and sI = 1.00 for the benzoate ion provides Lewis acidities LAI for 17 iodonium ions and Lewis basicities LBI and sI for 10 Lewis bases. The lack of a general correlation between the Lewis basicities LBI (with respect to Ar2I+) and LB (with respect to Ar2CH+) indicates that different factors control the thermodynamics of Lewis adduct formation for iodonium ions and carbenium ions. Analysis of temperature-dependent equilibrium measurements as well as ITC experiments reveal a large entropic contribution to the observed Gibbs reaction energies for the Lewis adduct formations from iodonium ions and Lewis bases originating from solvation effects. The kinetics of the benzoate transfer from the bis(4-dimethylamino)-substituted benzhydryl benzoate Ar2CH-OBz to the phenyl(perfluorophenyl)iodonium ion was found to follow a first-order rate law. The first-order rate constant kobs was not affected by the concentration of Ph(C6F5)I+ indicating that the benzoate release from Ar2CH-OBz proceeds via an unassisted SN1-type mechanism followed by interception of the released benzoate ions by Ph(C6F5)I+ ions.

Two transition-metal-free methods to access substituted phenols via the arylation of silanols or hydrogen peroxide with diaryliodonium salts are presented. The complementary reactivity of the two nucleophiles allows synthesis of a broad range of phenols without competing aryne formation, as illustrated by the synthesis of the anesthetic Propofol. Furthermore, silyl-protected phenols can easily be obtained, which are suitable for further transformations.

A visible light accelerated C–H functionalization reaction in palladium-catalyzed arylation of vinyl arenes with diaryliodonium salts is reported in the absence of additional photosensitizer. The kinetic isotope effect (kH/kD) was ch

A safe and scalable synthesis of diaryliodonium triflates was achieved using a practical continuous-flow design. A wide array of electron-rich to electron-deficient arenes could readily be transformed to their respective diaryliodonium salts on a gram scale, with residence times varying from 2 to 60 s (44 examples).

A new synthetic method was developed for the N-arylation of pyrazoles using diaryliodonium salts. The transformation does not require any transition-metal catalyst and provides the desired N-arylpyrazoles rapidly under mild reaction condition in the presence of aqueous ammonia solution as a mild base without the use of inert atmosphere. The chemoselectivity of unsymmetric diaryliodonium salts was also explored with large number of examples.

Cu(OTf)2-catalyzed diarylation of activated alkenes by using diaryliodonium(III) salts has been developed. With this method, arylated oxindoles can be easily accessed in good yields. Insights into the mechanism of copper-catalyzed arylations are discussed, and the findings are expected to help increase the level of understanding of catalytic arylations with diaryliodonium salts. Georg Thieme Verlag Stuttgart. New York.

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Symmetrical and unsymmetrical diaryliodonium triflates have been synthesized from both electron-deficient and electron-rich arenes and aryl iodides with mCPBA and triflic acid. A thorough investigation of the optimization, scope and limitations has resulted in an improved one-pot protocol that is fast, high-yielding, and operationally simple. The reaction has been extended to the direct synthesis of symmetrical iodonium salts from iodine and arenes, conveniently circumventing the need for aryl iodides.