Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

Novel optically active 1,3-aminoalcohols derived from D-glucal

A series of ethyl(phenyl) 6-amino-2,3,6-trideoxy--D-glucopyranosides (amino=piperidino (Pip), pyrrolidino (Pyr), azetidino (Az), Bu₂N) have been prepared from tri-O-acetyl-D-glucal to obtain catalysts for asymmetric synthesis and the starting compounds for the syntheses of other bidentate ligands.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 45–52, January, 2000.     

Synthesis and Structure of Some N-[3-(Het)aryl-2-propenylidene]trifluoromethylanilines

The reactions of 4-nitrocinnamaldehyde with trifluoromethylanilines in the presence of molecular sieves were studied, and a series of new aromatic and heterocyclic aldimines were synthesized. The molecular and crystal structure of some of them were determined by X-ray crystallographic analysis.     

IR-spectroscopic studies of the interaction of pyridine bases with vanadium and molybdenum oxides supported on magnesia

As shown by IR-spectroscopic studies, pyridine bases interacting with V₂O₅ and MoO₃ supported on MgO form hydrogen bonds with surface hydroxyls and coordinate bonds with V and Mo ions. The interaction of 2,6-dimethylpyridine adsorbed on the surface with oxygen leads to the formation of 6-methylpyridine-2-carboxaldehyde, whose formyl group interacts with surface hydroxyls.

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, V₂O₅ MoO₃, MgO, V Mo. 2,6- 6--2-, OH-.

     

Synthesis of N-Pyridylmethylidene-2-aminopyridines and their Methyl-substituted Derivatives in the Presence of Molecular Sieves

We have studied condensation of 2-, 3-, 4-pyridinealdehydes and 6-methylpyridine-2-aldehyde with 2-aminopyridine and its 3-, 4-, and 6-methyl derivatives in benzene in the presence of molecular sieves. The reactions occur even at room temperature to form the corresponding pyridyl-pyridyl azomethines, and also aminals. We have determined the optimal conditions for carrying out the processes with the aim of obtaining both types of products. We consider the characteristics of the mass spectra for the synthesized aldimines. We present the X-ray diffraction results for the two aminals.     

Infrared spectroscopic study of the interaction between furan and a vanadium oxide catalyst

The results of the infrared spectroscopic study of the interaction between furan and a vanadium oxide catalyst permit to suppose that the intermediates in furan oxidation are surface succinyl oxide and maleates.

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, , , - .

     

Addition of Me3SiCN to trifluoromethyl derivates of N‐(pyridylmethylidene) anilines catalyzed by Lewis acids

A series of novel Shiff bases (1a–h) was synthesized by condensation of pyridinecarboxaldehydes (1–4) with 3‐ and 4‐trifluoromethylanilines (5, 6) in the presence of molecular sieves (4 Å). It was found that AlCl₃ and AlBr₃ catalyzed the addition of Me₃SiCN to the C?N bond of the imines obtained, whereas the other Lewis acids studied (YCl₃, LaCl₃, ZnI₂) were not active. The reactivity of the imines in the title reaction, on the whole, correlated with their basicity. Besides the addition giving the expected α‐amino nitriles (2a,b,d–f,h), an unusual reaction leading to unsaturated nitriles (3a–h) was observed. The structures of saturated and unsaturated products 2d and 3c were determined by X‐ray diffraction. Copyright © 2001 John Wiley & Sons, Ltd.     

Synthesis and Structure of Some 2-Trifluoromethyl-substituted Hetarylmethylidene(or propylidene)anilines

The reaction of furan, thiophene, pyridine, and also furylacryloyl aldehydes with 2-trifluoromethylanilines has been studied in the presence of molecular sieves and a series of new heterocyclic aldimines has been synthesized. The molecular and crystalline structure of some of them were determined by X-ray structural analysis.     

Diastereoselective addition of trimethylsilyl cyanide to chiral O‐, S‐ and N‐heterocyclic aldimines

Systematic investigation of asymmetric trimethylsilylcyanation of heterocyclic azomethines has been realized. The addition of trimethylsilyl cyanide to optically active furan, thiophene and pyridine aldimines, derived from (R)‐ and (S)‐1‐phenylethylamine, was studied in the presence of Lewis acids, and a series of the corresponding α‐amino nitriles was obtained in fair to good yields (up to 91%). Unsaturated nitriles were also formed from pyridine imines. The sense of asymmetric induction and the degree of diastereoselectivity in the synthesis of α‐amino nitriles were determined by means of ¹H NMR. The stereochemical outcome is a result of the same sense of asymmetric induction: Re face attack to the (S)‐imines and Si face addition to the (R)‐imines took place. The (R,R)‐ (up to 81%) or (S,S)‐ (up to 87%) α‐amino nitriles predominated in the products obtained from the all furan, thiophene and pyridine (R)‐ or (S)‐imines respectively. Copyright © 2002 John Wiley & Sons, Ltd.     

Hydrosilylation Of Heterocyclic Aldimines Catalyzed By Transition Metal Complexes

The addition of triethylsilane to O- and S- heterocyclic Schiff bases in the presence of Rh, Pd, Pt, and Ir complexes has been studied. A series of the corresponding amines has been synthesized using the most active catalysts, which were the dimeric, monovalent complexes [Rh(1,5-cyclooctadiene)Cl]₂ and [Pd(allyl)Cl]₂.