The mechanism of the previously developed cross-coupling reaction of aryl Grignard reagents with aryl halides was explored in more detail. Single electron transfer from an aryl Grignard reagent to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle consists entirely of anion radical intermediates.

[reaction: see text] A one-pot protocol for converting 1,3- and 1,4-substituted aryl halides to arylamine boronate esters is described. This is achieved by sequential Ir-catalyzed aromatic borylation at the least hindered C-H bond of the aryl halide and subsequent Pd-catalyzed C-N coupling at the halide position of the crude arylboronic ester.

silica-grafted n-propyl-diaza-15-crown-5 (sgpdc) with immobilized palladium nanoparticles was found as an efficient heterogeneous catalytic system for the heck and suzuki coupling reactions and satisfied results were obtained. different derivatives of aryl halides and alkenes under the heck reaction were converted to the corresponding products with good efficiency. the presence of electron-dona...

We have successfully developed a novel cathodic cross-coupling reaction of aryl halides with arenes. Utilization of the cathodic single electron transfer (SET) mechanism for activation of aryl halides enables the cross-coupling reaction to proceed without the need for any transition metal catalysts or single electron donors in a mild condition. The SET from a cathode to an aryl halide initiates...

A regioselective Heck reaction of aliphatic olefins and aryl bromides is realized at internal carbons of olefins. Methanol solvent promoted halide ionization from neutral arylpalladium halide complexes via hydrogen bonding, so as to create cationic aryl-Pd species for regioselective olefin insertion.

Silica-grafted n-propyl-diaza-15-crown-5 (SGPDC) with immobilized palladium nanoparticles was found as an efficient heterogeneous catalytic system for the Heck and Suzuki coupling reactions and satisfied results were obtained. Different derivatives of aryl halides and alkenes under the Heck reaction were converted to the corresponding products with good efficiency. The presence of elec...

Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both C(aryl)-X and C(aryl)-CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic...

Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3 to Pd[P(t-Bu)3](Ar)(X) (X = Cl, Br, I). Conditions to observe the equilibrium between reductive elimination and oxidative addition were established ...

Density functional theory has been used to investigate various solvated species that may be formed from palladium bis N-heterocyclic carbene complexes, [Pd(cyclo-C{NRCH}2)2], (PdL2) in benzene solution. Formation of an g -arene complex is shown to stabilise a monocarbene species, PdL(g-C6H5X), where the arene is either the solvent or a reacting aryl halide. Oxidative addition of an aryl chlorid...

Aryl halides are common synthetic targets themselves, and also highly versatile synthetic intermediates. Aryl chlorides are much more widely available and easier to synthesise than the other halide derivatives, so the development of effective methods for interconverting aryl halide derivatives would therefore be extremely useful. This article outlines which transformations are particularly desi...