Nikolai V. Lukashev

The nickel-catalyzed Sonogashira–Hagihara reaction

Abstract The Sonogashira–Hagihara coupling of terminal acetylenes with aryl iodides in the presence of a nickel catalyst and CuI was investigated. The reaction proceeds rapidly in aqueous dioxane in the presence of Ni(PPh 3 ) 2 Cl 2 with high yields of disubstituted tolanes being obtained. The reaction seems to be an inexpensive alternative to the palladium-catalyzed process.

Bis(ferrocenyl)mercury as a source of ferrocenyl moiety in Pd-catalyzed reactions of carbon-carbon bond formation

Abstract The application of bis(ferrocenyl)mercury as a source of ferrocenyl group in Pd-catalyzed reactions with aryl halides, acid chlorides and electrophilic alkynes has been demonstrated. The formation of dimethyl-(Z)-2,3-di(ferrocenyl)-2-butenedioate in Pd-catalyzed addition of bis(ferrocenyl)mercury to dimethylacetylenedicarboxylate has been confirmed by X-ray analysis.

The successive substitution of halogens in 4-chloro-6-iodoquinoline by aryl groups in cross-coupling reactions with arylboronic acids

Abstract The conditions for selective stepwise substitution of iodine and chlorine atoms in 4-chloro-6-iodoquinoline which allow the synthesis of the corresponding diarylquinolines with different aryl groups in the 4- and 6-positions, in a one-pot procedure, in high yields are reported. A significant effect of the addition of water or Bu 4 NBr on the rate and yield of both stages was discovered.

Palladium-catalyzed cross-coupling reaction of bis(ferrocenyl)mercury with aryl iodides

Abstract Cross-coupling reactions of bis(ferrocenyl)mercury with aryl- and heteroaryl iodides were shown to be easy and convenient for the synthesis of monoarylsubstituted ferrocenes in high yields. The highly selective substitution of iodine atom in iodobromoarenes by the ferrocenyl unit was demonstrated.

The addition of phosphorus halides to ynamines. Ring-chain tautomerism of phosphirene with isomeric open structure

Abstract The reaction of halogenodiisopropylphosphines 3a-c with 1-diethylamino- 1-butyne 4 in dichloromethane leads to new phosphirenes 5. In benzene or pentane mixtures of phosphirines 5c and isomeric open structure 6 have been obtained. Ring-chain tautomerism for 5c and 6 have been observed for the first time.

Competitive addition and cycloaddition of low coordinated organophosphorus compounds to alkoxy- and aminoalkynes

Abstract Reactions of two- and three coordinated organophosphorus compounds with nucleophilic alkynes can proceed as competitive addition, [2+1]-, and [2+2]- cycloaddition reactions. Ring-chain tautomerism for phosphirenes and isomeric alkenylphosphines has been observed.

Cyanation of nucleophilic alkynes: easy approach to element-substituted α-cyanoenamines

Abstract The reactions of trimethylsilyl cyanide and tributyltin cyanide with ynamines proceeds as a regioselective syn -addition and provide previously unknown β-elementosubstituted α-cyanoenamines as pure E -isomers. The reaction of cyanogen bromide with ynamines as well the hydrocyanation of phosphorus substituted N , N -diethylaminoacetylenes by acetone cyanohydrin also proceeds as regioselective syn -addition, though the initially formed Z -isomers undergo an easy transformation into E -isomers. Cross-coupling reaction of β-bromo-α-cyanoenamine with arylboronic acids were shown to be an easy and convenient approach to α-dialkylaminosubstituted cynnamonitriles.

Synthesis of perhaloaromatic diethyl methylphosphonates containing α-electron-withdrawing group

Abstract The synthesis of new perhaloaryl(hetaryl)substituted methylphosphonates using nucleophilic aromatic substitution is described. Transformations of synthesized phosphonates into perhaloary(hetaryl)substituted methanes are presented.

Palladium-catalyzed copper(I) salt-mediated arylation of a bis(dimethylamino)phosphonyl-stabilized carbanion

Abstract The synthesis of new arylmethylphosphonic acid tetramethyl diamides by a palladium-catalyzed cross-coupling reaction of a bis(dimethylamino)phosphonylmethylcopper(I) reagent with aryl iodides is described.

Hydro- and silylcyanation of cholic acid derivatives. Synthesis of novel pincer ligands based on litocholic acid

Reactions of 3-oxo derivatives of cholic acid esters with acetone cyanohydrin and trimethylsilyl cyanide lead to exclusive or predominant formation of the corresponding 3-cyano-3-hydroxy and 3-cyano-3-trimethylsiloxy derivatives with axial orientation of the cyano group. Reduction of the cyano group in the addition products gives 3-aminomethyl derivatives which can be used to obtain pincer ligands containing two cholane fragments.