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Information × Registration Number 0316U004063, 0116U002364 , R & D reports Title Synthesis of new types of carbenes on the basis of imidazol-2-ylidenes, their fused analogues and their transition metal complexes. Study of catalysis by metal carbene complexes of the ketone and haloarene reduction. popup.stage_title Синтез нових типів карбенів на основі імідазол-2-іліденів, конденсованих аналогів та їх комплексів з перехідними металами. Вивчення каталізу карбеновими комплексами металів реакцій відновлення кетонів, галогенаренів. Head Korotkikh Nikolai Ivanovich, Доктор хімічних наук Registration Date 27-12-2016 Organization Institute of Organic Chemistry National Academy of Sciences of the Ukraine popup.description2 The object of the study is new types of stable carbenes on the basis of fused imidazol-2-ylidenes and their precarbene and carbenoid forms to obtain highly effective catalysts of organic reactions in homogenic and heterogenic processes. The goal of the work is synthesis of stable carbenes of new generation for using as catalysts of organic reactions (hydrodehalogenation of haloarenes, reduction of multiple bonds, transesterification, etc. Methods of the study are synthetic, spectroscopic (NMR spectroscopy), analytical (chromatography, elemental analysis), X-ray analysis. The results of the research involve synthesis of sterically shielded and sterically open derivatives of phenanthro[9,10-d]imidazol-2-ylidenes with adamantyl, methyl and 2,6-diisopropylphenyl substitutents starting from phenathrenequinone. Methyl derivatives of carbenoids were synthesized by the reaction of phenathrenequinone with ammonium acetate and formaldehyde followed by the subsequent methylation of the obtained phenanthro[9,10-d]imidazole with dimethyl carbonate in the presence of DABCO, methylation of the intermediate 1-methylphenanthro[9,10-d]imidazole with methyl iodide and generation of 1,3-dimethyl-phenanthro[9,10-d]imidazol-2-ylidene under the action of sodium tert-butoxide on the corresponding salt in the presence of copper iodide. Adamantylation of phenanthro[9,10-d]imidazole was carried out in dichlorobenzene in the presence of calcium hydride. Mono- and disubstituted derivatives of this system were prepared. Synthesis of dipp-substituted phenanthro[9,10-d]imidazolium salt was developed using the reaction of phenanthrenequinone, respective diimine and chloromethylmethyloxide, the synthesis of palladium iodide complex on their basis was performed. The DFT calculations of singlet-triplet splittings were carried out for a series of carbenes and the most stable ones were defined. The resulting data have prospects for the development of preparative synthesis of stable carbenes, precarbenes and their derivatives, catalysis of organic reactions with the help of the indicated compounds. The area of the application is synthesis of stable carbenes and their derivatives, catalysis of organic reactions. Product Description popup.authors Єня Василь Іванович Кнішевицький Артур Володимирович Околовська Анастасія Геннадієвна Сабєров Вагіз Шамільйович Сидякін Данило Вадимович popup.nrat_date 2020-04-02 Close