V. A. Dokichev

SYNTHESIS AND BIOLOGICAL ACTIVITY OF N-(2-HYDROXYETHYL)CYTISINE DERIVATIVES

Derivatives of N-(2-hydroxyethyl)cytisine, N-(2-hydroxypropyl)-, N-(2-hydroxy-2-(1-adamantyl)ethyl)-, and N-(2-hydroxy-2-phenylethyl)cytisine, were synthesized by reduction of N-(2-oxopropyl)-, N-(2-oxo-2-(1-adamantyl)ethyl)-and N-(2-oxo-2-phenylethyl)cytisine with metal hydrides. The antiarrhythmic and analgesic activities of the prepared compounds were investigated.

Reduction of substituted spiro[cyclopropane-3-(1-pyrazolines)] to spiro[cyclopropane-3-pyrazolidines] and 1-(2-aminoethyl)cyclopropylamine derivatives

Raney nickel-catalyzed hydrogenation of 5-substituted spiro[cyclopropane-3-(1-pyrazoline)]-5-carboxylates occurs with N—N bond cleavage with simultaneous cyclocondensation to give 3-aminopyrrolidin-2-ones containing a spirocyclopropane fragment. The presence of the second ester group in the pyrazoline side chain, in the position ensuring the formation of a five-membered ring results in 6,11-diazadispiro[2.1.4.2]undecane-7,10-dione, the product of double cyclocondensation of the intermediate diamine. Hydrogenation of the aryl-substituted spiro[cyclopropane-3-(1-pyrazolines)] in the presence of acetone affords hexahydrospiro[cyclopropane-4-pyrimidines], which can be converted into the cyclopropane-containing 1,3-diamines in the individual state or as salts.

Reactions of diazoalkanes with unsaturated compounds 15.* Catalytic reactions of unsaturated carbonyl compounds and their derivatives with diazomethane**

The present study concerned with the influence of the nature of the acetal fragment in unsaturated compounds on the reactivity of the C=C bond in cyclopropanation reactions with diazomethane catalyzed by copper and palladium compounds. The acetal substituents at the α- or γ-position with respect to the C=C bond were found to exert an activating effect on the yields of cyclopropanation products compared to the starting unsaturated carbonyl compounds, which give 1,3-dipolar cycloaddition adducts with CH2N2 as by-products. Cyclopropanation of the double bonds appeared to be most efficiently catalyzed by Pd(acac)2.

One-step synthesis of substituted 3,5-dinitropiperidines and 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonanes from 1,3-dinitropropanes

Abstract1,5-Dinitro-3,7-diazabicyclo[3.3.1]nonane derivatives were synthesized in up to 83%yields by the Mannich reaction of 1,3-dinitropropanes with excess formaldehyde and primary amines. In some cases, for instance, when 2,2-dimethyl-1,3-dinitropropane and benzylamine or monoethanolamine are used, the reaction occurs with low yields or stops at the step of formation of 3,5-dinitropiperidines. The influence of the structure of the starting compounds and reaction conditions on the yields of 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonanes and 3,5-dinitropiperidines was studied.

Reaction of γ-nitroketones and methyl 4-nitrobutanoates with formaldehyde and primary amines

Abstract5-Nitropentan-2-one reacts with methylamine and formaldehyde according to the Mannich reaction pattern to give 5-hexahydropyrimidinylcarbonyl-substituted 1-nitro-3,7-diazabicyclo[3.3.1]nonane in one experimental stage. When methyl 3-R-4-nitrobutanoates are used, the reaction stops after the formation of substituted 5-nitrohexahydropyrimidines in 40–98% yields.

Synthesis of N3-substituted methyl exo-3,4-diazatricyclo[5.2.1.02,6]dec-4-ene-5-carboxylates

Reactions of methyl exo-3,4-diazatricyclo[5.2.1.02.6]dec-4-ene-5-carboxylate with methyl diazoacetate, methyl iodide, ethylene oxide, acetic acid, nitrosonium cation, and sulfur led to the formation of a series of N3-substituted exo-3,4-diazatricyclo[5.2.1.02,6]dec-4-enes.

Synthesis of Optically Active Methyl 12-Oxo-9,10-epoxyoctadecanoate

The procedure for synthesizing optically active methyl 12-oxo-9,10-epoxyoctadecanoate (enantio- meric purity ∼90%) was developed, starting from ricinolic acid methyl ester.

Rh2(OAc)4-catalyzed reaction of 1,3-dioxanes with methyl diazoacetate

The reactions of methyl diazoacetate with 1,3-dioxanes in the presence of Rh2(OAc)4 afford 1,4-dioxepanes in up to 46% yields. The insertion of methoxycarbonylcarbene into the C—O bond occurs only in the case of 2-phenyl-1,3-dioxanes.

ZrCl4-Catalyzed scission of ethylene acetals with organoaluminum compounds

Ethylene acetals and ethylene ketals undergo reductive scission under the action of Bui2AlH in the presence of catalytic amounts of ZrCl4. With Et3Al and Bui3Al, reductive alkylation also occurs.

Interaction of diazoalkanes with unsaturated compounds

The stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of Cu, Pd, and Rh compounds has been studied. Stereoselectivity of the cyclopropanation depends on the nature of the transition metal and does not depend on its valent state or ligand environment. The reaction proceeds predominantly asexo-cycloaddition of the methylene fragment. The greatest amount ofendo-isomer (up to 47 %) is formed in cyclopropanation of norbornadiene andexo-tricyclo[3.2.1.02,4]oct-6-ene in the presence of Cu and Rh compounds.