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Information × Registration Number 0214U008451, 0110U000002 , R & D reports Title The reactions of condensation, heterocyclization and recyclization of keto- and thioamide compounds of linear and cyclic structure with nucleophilic reagents popup.stage_title Head Volochnyuk Dmytro Mikhalovich, Registration Date 24-12-2014 Organization Institute of Organic Chemistry National Academy of Sciences of the Ukraine popup.description2 The work is related to study of condensation, heterocyclization and recyclization reactions of keto- and thioamide compounds of linear and cyclic structure with nucleophiles. It was found that reaction of N-alkylhydrazones of aliphatic ketones with Vilsmeyer - Haack reagent (DMF - POCl3) is a promising approach to the synthesis of trisubstituted unsymmetric pyrazoles. It was found that either 1,3,4-trialkylpyrazoles or 1,3-dialkylpyrazole-4-carbaldehydes can be obtained in these transformations with high yields (72-83%) and in a regioselective manner. Reactions of N-alkylhydrazones derived from active methylene compounds having electron-withdrawing substituent (R2= CO2Et, CN, p-TolSO2, (PPh3)+, NPht), as well as hydrazones derived from electron-deficient ketones (R1=CF3, CO2Et, C(O)Me) with Vilsmeyer - Haack reagent were studied. It was found that increasing the electron-withdrawing properties of the substituent at alfa-CH2 moiety diminished yield of the products derived from electrophilic attack at alfa-CH3 group. Scope and limitations of reaction of 2,2,2-trifluorodiazoethane with corresponding alkenes/alkynes were studied; relationship between the nature of the substituents in the substrates and reaction rate was demonstrated. It was found that copper(I) chloride-catalyzed trifluoromethylcyclopopanation of the corresponding cyclic enamides upon action of 2,2,2-trifluorodiazoethane is a convenient method for the synthesis of trifluoromethyl-substituted bicyclic amines derived from 2-azabicyclo[2.1.0]pentane, 2-azabicyclo[3.1.0]hexane and 2-azabicyclo[3.1.0]heptane cores. The chemical space covered by conformationally restricted diamines (CRDA) was analyzed. A simple mathematical model for description of this space was proposed; the model was shown to correlate with experimental data. Based on the results of this analysis, novel and hardly accessible representatives of CRDA were outlined and aimed for synthesis. Among these representatives, synthetic approaches to amino azabicyclo[n.3.1]alkanes, bridged 1,4-diazepanes, 5- and 6-amino-2-azanorbornanes, diaminocyclobutanes and diaminospiro[3.3]heptanes were developed. It was found that 1-aminospiro[3.3]heptan-1,6-dicarboxylic acids are concurrent inhibitors of glutamate racemase (RACE) from Bacillus subtilis, which can be used as the starting point for discovery of novel antibacterials. An unusual rearrangement of 1-oxa-6-azaspiro[2.5]octane derivatives to give novel 5-substituted 2-azabicyclo[3.1.0]hexanes was found. Product Description popup.authors Івонін Сергій Павлович Артамонов Олексій Сергійович Брицун Василь Миколайович Горлова Аліна Олексіївна Зарудницький Євген В'ячеславович Коробко Сергій Володимирович Короткий Юрій Васильович Курпіль Богдан Богданович Нагірняк Павло Ігорович Пушкарьов Павло Анатолійович Ратушна Ніна Іванівна Сібгатулін Дмитро Олександрович Самойленко Людмила Сергіївна Смалій Радомир Володимирович Субота Андрій Іванович Таіров Максим Олександрович Федюк Дмитро Володимирович Чуйко Олексій Леонідович popup.nrat_date 2020-04-02 Close