R. G. Kostyanovskii

Asymmetric nitrogen 60. Acylation as a pathway to optically active 1,3,3-trisubstituted diaziridines

Conclusions1.The acylation of 1,3,3-trisubstituted diaziridines with acyl chlorides is realized primarily at the substituted N1 atom and is accompanied by diaziridine-hydrazone rearrangement.2.Acylation with a 0.5-mole amount of (S)-N-tosylproline chloride is an effective method for the optical activation of 1,3,3-trialkyldiaziridines and can be used to determine the absolute configurations of these compounds.

Geminal systems. Communication 28 Alcoholysis of N-chloro-N-alkoxyamides and synthesis of N,N-dialkoxyureas

Conclusions1.N-Chloro-N-alkoxysulfonamides and N-chloro-N-alkoxyphosphoamides have chlorinating properties in the reaction with triethylamine in methanol.2.N-Chloro-N-alkoxyureas were synthesized for the first time, and from them previously unknown N,N-dialkoxyureas were obtained by nucleophilic substitution reactions.

Geminal systems: 19 Reactions of aminomethylphosphines with electrophilic reagents

Conclusions1.In the reactions of aminomethylphosphines with the acylating reagents RCOCl, ClCN, and PhNCO the electrophilic attack is carried out at the phosphorus atom with cleavage of the C-P bond and the formation of acyl-, cyano-, and carbamoylphosphines.2.Aminomethylphosphines display dual reactivity with respect to alkylating reagents. The attack of MeI is directed at the phosphorus atom to form aminomethylphosphonium salts, where as PhCH2Br, MeOSO2F, and HCl react at the nitrogen atom, producing phosphinomethylammonium salts. The regiospecificity of the reaction depends on the basicity of the N atom, the size of the substituents on the P atom, and the type of alkylating reagent.

ASYMMETRIC NITROGEN .57. INVESTIGATION OF THE STEREOCHEMISTRY OF AZIRIDINECARBOXYLIC ACID-DERIVATIVES BY NMR

ConclusionsThe preferred trans configuration of 1,2-disubstituted aziridines and cis configuration of NH-aziridine-2-carboxylic esters were established by means of the1H and13C NMR spectra and the two-dimensional NOESY and COSY-45 spectra.

Oligomers of aziridines and N-?-aziridinoethylamides

Conclusions1.An efficient method of aziridine dimer synthesis is presented involving reaction of aziridine with esters of strong organic acids followed by alkaline hydrolysis of the resultant N-acyl derivatives.2.New N-acyl and carbamoyl derivatives of aziridine dimer and trimer were synthesized.3.Linear and branched isomers of aziridine tetramer and also diastereomers of 2-methylaziridine dimer were isolated and characterized.4.An efficient regiospecific synthesis of 2,2-dimethylaziridine dimer and trimer was developed.

Asymmetric nitrogen Communication 48. Geminal systems. communication 32 NH-dialkoxyamines: synthesis, mydroxy-and aminomethylation, nmr spectra, and configurational stability

Conclusions1.Alkaline hydrolysis of N,N-dialkoxy-N′,N′-dimethylureas gives NH-dialkoxyamines.2.N-Hydroxymethyl- and N-aminomethyl-N,N,-dialkoxyamines have been synthesized and their reactions with nucleophiles and electrophiles have been studied.3.The configurational stability of the N atom in NH-dialkoxyamines and their derivatives has been determined by NMR.

Reactions of N-, P-, S-, and As-nucleophiles with cyanoacetylene

Conclusions1.High trans-stereospecificity has been shown in the addition to cyanoacetylene of: a) secondary aliphatic amines, with cooling, and b) under the usual conditions with sterically hindered amines, phosphines, mercaptan, and arsine, and also with amines with reduced positive mesomeric capacity of the nitrogen atom.2.The cis-products of the addition to cyanoacetylene of aziridines, diaziridine, imidazole, di-tert-butylamine, phosphines, and arsine are highly resistant to cis-trans isomerization. In cis-β-di-tert-butylaminoacrylonitrile, amide-type conjugation is sterically hindered.

Geminal systems. Communication 29. Reactions of N-chloro-N-methoxy-N′,N′-dimethylurea with N-nucleophiles

ConclusionsIn the reaction of N-chloro-N-methoxy-N′,N′-dimethylurea with amines, a nucleophilic substitution of the chlorine atom at the N atom takes place to form N-alkoxyhydrazines, which are stable in the reaction with Me3N, pyridine, toluenesulfonamides, and give products of further transformations with Me2NH and MeONHMe.

Absolute configuration of diastereomeric derivatives of N-substituted aziridine-2-carboxylic acids

Individual diastereomers of a number of anilides of N-substituted aziridine-2-carboxylic acids have been obtained. Conclusions regarding the spatial structure of the compounds indicated have been drawn on the basis of the 1H NMR, 15N NMR, and CD spectra.

Determination of configuration of products of nucleophilic addition to activated acetylenes by the NMR method

ConclusionsIt was shown that the stereospecificity of SSCC3C,Htrans > 3JC,Hcis is applicable as a configurational test for di- and trisubstituted alkenes R2E(Y)C=C(X)H with various heteroatomic substituents (E=N, P, S) and activating groups (X=CO2Alk, CN at Y=H, and X=Y=CO2Alk, CN, CF3).