Dmitry A. Gruzdev

Synthesis of enantiomers of 6-nitro- and 6-amino-2-methyl-1,2,3,4-tetrahydroquinolines

Enantiomers of 2-methyl-6-nitro-1,2,3,4-tetrahydroquinoline have been obtained by kinetic resolution of racemic 2-methyl-1,2,3,4-tetrahydroquinoline in acylation with acyl chlorides of N-protected amino acids followed by regioselective nitration of the diastereoisomeric amides and acidic hydrolysis. The introduction of a trifluoroacetyl protecting group into the position 1 of the enantio pure nitro compound followed by the reduction led to (S)-6-amino-2-methyl-1-trifluoroacetyl-1,2,3,4-tetra-hydroquinoline in a high yield.

N-Tosyl-(S)-Prolyl Chloride in Kinetic Resolution of Racemic Heterocyclic Amines

The kinetic resolution of racemic heterocyclic amines via acylation with N-tosyl-(S)-prolyl chloride was systematically investigated. It was established that racemic mixtures of aromatic amines could be resolved with high efficiency, while the acylation of 2- and 3-methylpiperidines occurred with low diastereoselectivity. A method for the preparation of enantiomerically pure (3R)-7,8-difluoro-3-methyl-3,4-dihydro-2H-[1,4]benzoxazine was developed.

Diastereoselective Acylation of Racemic Heterocyclic Amines with N-Tosyl-(S)-Prolyl Chloride and its Structural Analogs

A comparative study on the kinetic resolution of racemic amines (2,3-dihydro-4H-1,4-benzoxazine and 1,2,3,4-tetrahydroquinoline derivatives) via diastereoselective acylation with N-tosyl-(S)-prolyl chloride and its structural analogs was performed. The effect of resolving agent structure on the stereoselectivity of heterocyclic amine acylation was examined. The highest stereoselectivity was achieved in the case of acylation with acyl chlorides bearing a conformationally restricted pyrrolidine ring and an aromatic substituent in the protecting group at the nitrogen atom.

Piezoelectric and ferroelectric properties of organic single crystals and films derived from chiral 2-methoxy and 2-amino acids

ABSTRACT Local piezoelectric and ferroelectric properties as well as morphology of single crystals and films of two novel chiral organic compounds derived from chiral 2-methoxy and 2-amino acids have been investigated. The crystals demonstrated piezoelectric response exceeding that of lithium niobate. The piezoelectric response was registered also in compound films. Piezoelectric properties and domain structure of single crystals and films have been studied by piezoresponse force microscopy.

Synthesis of ortho-carboranyl derivatives of (S)-asparagine and (S)-glutamine

Abstract(S)-Asparagine and (S)-glutamine ortho-carboranyl derivatives with free amino and carboxy groups in the α-position were synthesized. By an example of Nγ-(1,2-dicarba-closo-dodecarboran-3-yl)-(S)-glutamine it was demonstrated that the developed synthetic approach carboranyl derivatives of amino acids allowed the preparation of optically pure isomers.

Morphology and piezoelectric characterization of thin films and microcrystals of ortho-carboranyl derivatives of (S)-glutamine and (S)-asparagine

ABSTRACT Local morphological features and piezoelectric properties of films and bulk crystals of ortho-carboranyl derivatives of (S)-asparagine and (S)-glutamine have been investigated at nanoscale by atomic force and piezoresponse force microscopies. Both films and bulk crystals of the studied compounds demonstrated a very high piezoelectric response exceeding that of lithium niobate. The crystal structure has been studied by single crystal X-ray diffraction.

Synthesis and antimycobacterial activity of N-(2-aminopurin-6-yl) and N-(purin-6-yl) amino acids and dipeptides

Synthetic routes to novel N-(purin-6-yl)- and N-(2-aminopurin-6-yl) conjugates with amino acids and glycine-containing dipeptides were developed. In vitro testing of 42 new and known compounds made it possible to reveal a series of N-(purin-6-yl)- and N-(2-aminopurin-6-yl) conjugates exhibiting significant antimycobacterial activity against Mycobacterium tuberculosis H37Rv, Mycobacterium avium, Mycobacterium terrae, and multidrug-resistant M. tuberculosis strain isolated from tuberculosis patients in the Ural region (Russia). N-(2-Aminopurin-6-yl)- and N-(purin-6-yl)-glycyl-(S)-glutamic acids were the most active compounds.

Synthesis and piezoelectric properties of N -phthaloylglutamic acid derivatives

The (S,S)- and (R,R)-enantiomers of dimethyl 2,4-diphthalimidoglutarate were synthesized by nucleophilic substitution of bromine in dimethyl (2S,4RS)-4-bromo-N-phthaloyl-glutamate upon treatment with potassium phthalimide, followed by separation. The crystal structure of the obtained compounds was studied by X-ray diffraction. Crystals of enantiomerically pure dimethyl 4-hydroxy- and 4-phthalimido-N-phthaloylglutamates were found to possess a noticeable piezoelectric activity.

Synthesis of enantiomers of N-(2-aminopurin-6-yl)amino acids

Nonracemic N-(2-aminopurin-6-yl)-substituted amino acids were synthesized by nucleophilic substitution of chlorine atom in 2-acetamido-6-chloropurine upon treatment with amino acid tert-butyl esters and subsequent removal of protecting groups. Their enantiomeric composition was determined by HPLC on chiral stationary phases.

Synthesis of purine and 2-aminopurine conjugates bearing the fragments of heterocyclic amines at position 6

A series of novel N-(purin-6-yl)- and N-(2-aminopurin-6-yl) derivatives of heterocyclic amines was synthesized. It was found that preferred preparative method for N-(purin-6-yl) derivatives of heterocyclic amines is interaction of 6-chloropurine with heterocyclic amines without any catalyst; whereas N-(2-aminopurin-6-yl) derivatives were obtained in the moderate-to-high yields while heating 2-amino-6-chloropurine and heterocyclic amines in water in the presence of sulfuric acid.