T. P. Tolstaya

Catalytic coupling of terminal acetylenes with iodoarenes and diaryliodonium salts in water

Abstract The catalytic coupling of terminal acetylenes with iodoarenes and diaryliodonium salts are shown to occur in aqueous K 2 CO 3 in the presence of 10 mol.% Bu 3 N under very mild conditions using PdCl 2 (PPh 3 ) 2 and CuI as catalyst precursor to give substituted tolans in high yields.

Palladium-catalyzed arylation of styrene and acrylic acid in water

Abstract Palladium-catalyzed arylations of styrene and acrylic acid are shown to occur in the presence of base (Na2CO3 or K2CO3) in pure water using simple palladium compounds as catalyst precursors.

The reactions of phenyl(B-carboranyl)iodonium salts with nucleophiles

Abstract The reactions of phenyl(9-o-carboranyl)-, phenyl(9-m-carboranyl)- and phenyl(2-p-carboranyl)-iodonium salts with the nucleophiles F−, Cl−, Br−, OH−, C5H5N, Hg and CN− were studied. Depending on the nature of the nucleophile and the carborane ligand in each iodonium compound, these reactions either proceed as nucleophilic substitution or via a radical mechanism. Nucleophilic substitution, which takes place at the boron atom, of the carborane nucleus only, gives “carboranylation” products of nucleophiles. Free-radical processes are characterized by breaking of the CI+ bonds with the formation of phenyl radicals and their transformation products. The reasons for such an unusual behaviour of phenyl(B-carboranyl)iodonium salts in reactions with nucleophilic agents are discussed in the light of the results obtained and previous results.

Arylation of anions with diarylhalonium fluoroborates under conditions of interphase catalysis

Conclusions1.Arylation of anions by diarylhalonium fluoroborates under conditions of interphase catalysis proceeds more rapidly than in homogeneous media and as a rule in higher yield of the desired products.2.The rules for the influence of substituents in the aromatic ligands of the iodoniura salts on their reactivity are retained on going over from homogeneous media to a two-phase system.3.The yield of O-phenylation products grew in the series

Nucleophilic substitution in the 10,11-dihydrodibenz[b,f]iodepinium cation

Ph_2 \mathop I\limits^ +< Ph_2 \mathop {Br}\limits^ +< Ph_2 \mathop {Cl}\limits^ +

Phenyl-2-carboranyliodonium fluoborate

in the reaction of diphenylhalonium cations with the benzenesulfinate anion.

Synthesis of reactive organotin dichlqrides from organomercury compounds and SnCl2 in dimethoxyethane

ConclusionsThe triphenyloxonium cation is brominated only in the presence of anhydrous AgBF4 in which the first Br atom enters into each benzene ring almost exclusively in the para position to the onium center, but the tris(4-bromophenyl)oxonium cation thus formed is readily brominated further under the same conditions with the formation of tris(3,4-dibromophenyl) oxonium borofluoride.

Reaction of triaryloxonium salts with bases via dehydroarenes

Abstract10,11-Dihydrodibenz[b,f]iodepinium tetrafluoroborate gave only 1-(2-azidophenyl)-2-(2-iodophenylethane with the N3− in aqueous DMSO, while with NO2− it gave 1-(2-nitrophenyl)-2-(2-iodophenyl)ethane (93%), 9,10-dihydrophenanthrene (5%), and traces of phenanthrene. Both in pure and aqueous DMSO this cation with the Br− ion was converted into phenanthrene (80% and 68% respectively) and 1-(2-bromophenyl)-2-(2-iodophenyl)ethane (10 and 20%), while in water it gave 9,10-dihydrophenanthrene (75%) and phenanthrene (5%). A new route for the synthesis of 1-(2-aminophenyl)-2-phenylethane starting from this tetrafluoroborate has been proposed.