Optically active (2-aminomethylferrocenyl) phosphines with the phosphorus chiral center

The reaction of an enantiomeric planar-chiral palladium derivative of dimethyl-aminomethylferrocene with PhMePLi in THF at room temperature afforded a 1.5∶1.0 mixture of diastereomeric aminophosphines containing the phosphorus asymmetrical center along with a chiral plane. The absolute configuration of the phosphorus atom was determined based on the X-ray diffraction data for the complex of the minor diastereomer with PdI₂. The presence of the (S)-chiral plane in the initial palladium compound favors the predominant formation of the product with the (S)-configuration of the phosphorus center.     

Synthetic approaches to trialkyl(ferrocenylmethyl)ammonium salts as cationic templates for the preparation of ferromagnets on the basis of bimetal oxalates

Trialkyl(ferrocenylmethyl)ammonium salts and their 2-substituted analogs designed for the preparation of molecular ferromagnetics based on bimetallic oxalates were synthesized using classical alkylation of dialkylaminomethylferrocenes by alkyl halides and nucleophilic substitution reaction of 2-substituted dimethylaminomethylferrocene methiodides with trialkylamines. In the case of salts with electron-donating substituents in position 2, only the latter of the two proposed routes is applicable because N-alkylation with alkyl halides is accompanied by competing ferrocenylmethylation of the starting amine. On the contrary, the salts with electron-withdrawing 2-substituents should be prepared preferably by the reaction of amines with alkyl halides, while nucleophilic trialkylamination of methiodides is complicated by deprotonation induced by bases.     

Diatomic phenols as nucleophilic components in the carbonylation of the chelated C,N-palladacycle of the ferrocene series

The carbonylation of the chelated palladium derivative of dimethylaminoferrocene in the presence of diatomic phenols affords mixtures of the corresponding mono- and diacylated dihydroxybenzenes containing a 2-dimethylaminomethylferrocenyl fragment in the acyl moiety.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2756–2758, December, 2004.     

Synthesis and electrochemical properties of mono- and (±)-1,2-dialkylferrocenes and alkylferrocenium hexafluorophosphates in aqueous and micellar media

Absract Simple methods have been developed for the preparation of a series ofn-alkylferrocenes H(CH₂) _n Fc (n = 3, 5–8, or 12) based on Friedel-Crafts acylation of ferrocenes followed by reduction of the corresponding ketones with Zn amalgam. The properties of H(CH₂) _n Fc and the corresponding ferrocenium ions in micellar aqueous solutions and the behavior of water-soluble cations H(CH₂) _n Fc⁺ in the absence of micelles were studied by cyclic voltammetry. In all cases, the formal redox potentials of ferrocenes (E ^o) increase linearly asn increases up to 8. Whether micelles are present or not, the corresponding correlation equation has the following form:E ^o= + n, where = 29 mV in all cases. The synthesis of (±)-1-ethyl-2-methylferrocene from racemic -dimethylaminoethylferrocene is reported.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2575–2581, October 1996.     

Stereochemical control in reactions of chiral ketone with 2-lithiated substituted ferrocene derivatives

The formation of a new chiral center in the reactions of ketone 4-MeOC₆H₄CH(Et)C(O)Et with planar-chiral 2-lithio-1-methyl- and 1-chloro-2-lithioferrocenes proceeded stereoselectively to give two diastereomers in a ratio of 3 : 2 or a single diastereomer, respectively, out of four possible diastereomeric 4-aryl-3-ferrocenylhexan-3-ols. The replacement of the hydroxy group in the resulting compounds by hydrogen under the conditions of ionic hydrogenation was studied. The configurations of the reaction products were established by X-ray diffraction analysis and ¹H NMR spectroscopy.