Solvent-Free Mechanochemical Synthesis of Aryl Glycosides[ 1 ]

Aryl glycosides have been prepared from a range of readily available glycosyl halides by a solvent-free mechanochemical procedure employing a planetary ball mill in excellent yields. Besides being a solvent-free reaction, the procedure has been successful in eliminating the need for employing any phase-transfer catalyst in the reaction.     

Copper-mediated cyanation reactions

Aryl nitriles can be efficiently synthesized through transition-metal-mediated cyanation of aryl halides, arenes, aryl boronic acids, and so on. Among those most commonly used transition-metals, copper catalysts are surely much more inexpensive and easier to handle, compared to any other metal catalysts. Considering the high-efficiency of copper catalysts in the activation of C–X, C–H, and C–B bond as well as in the formation of C–CN bond, this Letter summarizes various copper-mediated cyanations based on the different kinds of cyanide reagents, such as metal cyanides, potassium hexacyanoferrate(II), acetone cyanohydrins, DDQ, AIBN, benzyl cyanide, malononitrile, nitromethane, and DMF. Our group’s recent contributions to this area are also demonstrated.     

Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides

A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.     

Catalyst-free one-pot synthesis of benzimidazoles from 1,2-diaminoarenes and alcohols

A new and efficient protocol is described for the one-pot synthesis of benzimidazoles from a variety of aryl alcohols and 1,2-diaminoarenes. The yields were ranging from moderate to excellent. Moreover, the present method is utilizing alcohols instead of aldehydes and the reactions are carried out under solvent- and catalyst-free conditions, offering an environmentally benign process.     

Facile and convenient synthesis of aryl hydrazines via copper-catalyzed C–N cross-coupling of aryl halides and hydrazine hydrate

An efficient and convenient method for the synthesis of aryl hydrazines has been developed via copper-catalyzed cross-coupling of aryl bromides and hydrazine with a readily accessible ligand and water as a solvent. The multigram scale procedure is applicable to aryl bromides bearing both moderately electron-donating and electron-withdrawing substituents in the aromatic nucleus. No column chromatography is required to obtain aryl hydrazine hydrochlorides in good yields.     

Synthesis of aryl azides from aryl halides promoted by Cu2O/tetraethylammonium prolinate

An efficient approach to aryl azides, in short reaction times and good to excellent yields, has been developed via the reaction of aryl halides with sodium azide under Cu₂O/tetraethylammonium prolinate catalysis.     

Pd-catalyzed assembly of phenanthridines from aryl ketone O-acetyloximes and arynes through C–H bond activation

Pd-catalyzed annulation of aryne and aryl ketone O-acetyloxime via C–H bond activation was realized. Through the C–H bond activation/insertion/cyclization/elimination reaction sequence, phenanthridines are successfully constructed, providing an attractive strategy to approach substituted heterocycle without preactivation of starting materials.     

Copper-catalyzed N-arylation of 2-arylindoles with aryl halides

10 mol% Cul combined with the DMEDA ligand can efficiently catalyze the N-arylation of 2-arylindoles with aryl iodides and aryl bromides in good to excellent yields. The aryl halides bearing electron-rich or electron-deficient functional groups can be well tolerated under this mild reaction conditions.