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Synthesis of Ruthenium Catalysts with a Chiral Arene Ligand Derived from Natural Camphor
Synthesis. 2022. Vol. 54. No. 21. P. 4721-4726.
Ruthenium complex with chiral arene ligand [(camphor-arene)RuCl2]2 was synthesized by the reaction of RuCl3∙nH2O with the chiral diene, which was obtained from natural camphor in 3 steps. This complex catalyzed asymmetric hydrogenation of acetophenone (64-85% ee), but decomposed in the catalytic reactions involving C-H activation of 2-phenyl-pyridine or benzoic acid derivatives.
Ankudinov N., Denis A. Chusov, Nelyubina Y. et al., Angewandte Chemie - International Edition 2021 Vol. 60 No. 34 P. 18712-18720
A new method for the synthesis of chiral diene rhodium catalysts is introduced. The readily available racemic tetrafluoro-benzobarrelene complexes [(R 2 -TFB)RhCl] 2 were separated into two enantiomers via selective coordination of one of them with the auxiliary S -salicyl-oxazoline ligand. One of the resulting chiral complexes with an exceptionally bulky diene ligand [( R,R ...
Added: January 24, 2023
Kolos A., Nelyubina Y., Evgeniya S. Podyacheva et al., Dalton Transactions 2023 Vol. 52 No. 45 P. 17005-17010
The rhodium complex [(C5H2tBu2CH2tBu)RhCl2]2 with an asymmetric cyclopentadienyl ligand was prepared in 95% yield by the reaction of [(cod)RhCl]2 with tert-butylacetylene in the presence of AlCl3. A similar reaction in the presence of InBr3 gave the cationic fulvene complex [(C5H2tBu2=CHtBu)Rh(cod)]InBr4 (70%), which can add alcohols ROH and produce the more bulky catalysts [(C5H2tBu2CH(OR)tBu)RhCl2]2. The enantiomers ...
Added: November 23, 2023
Fatkulin A., Afanasyev O., Tsygankov A. et al., Journal of Catalysis 2022 Vol. 405 P. 404-409
Catalytic reductive reactions are essential for laboratory and industrial-scale organic synthesis. However, the nowadays trend is the development of new, progressively more complicated reducing systems, which hinders the application of such highly efficient approaches in practice. Another way to achieve highly active systems is enhancing the activity of the earlier developed catalysts with simple structures. ...
Added: January 11, 2022
Fateeva A., Shutkov I., Mazur D. et al., Mendeleev Communications 2022 Vol. 32 P. 186-188
Preparation of novel imidazole ligands containing
3-(benzyloxy)pyridinone moiety is described. The Ruiii and
Ruii leader-compounds containing the above-mentioned
ligands were synthesized by coordination of imidazole group.
The stability of the obtained compounds was explored in
buffer solution and in the presence of DMSO, respectively,
and their antiproliferative activity was assessed. ...
Added: January 19, 2024
Trifonova E., Ankudinov N., Denis A. Chusov et al., Chemical Communications 2022 Vol. 58 No. 47 P. 6709-6712
Asymmetric cyclopropanation of alkenes by aryldiazoacetates was achieved using the readily-available racemic (diene)rhodium complex in combination with the chiral oxazoline-phenol ligand, which acts as the chiral poison and selectively inhibits one of the enantiomers of the catalyst. This approach eliminates a common problematic step of the synthesis of the chiral catalysts. ...
Added: January 24, 2023
Larionov V., Yashkina L., Medvedev M. et al., Inorganic Chemistry 2019 Vol. 58 No. 16 P. 11051-11065
Chiral copper(II) and cobalt(III) complexes (1–5 and 6, respectively) derived from Schiff bases of (S)-2-(aminomethyl)pyrrolidine and salicylaldehyde derivatives were employed in a mechanistic study of the Henry reaction-type condensation of nitromethane and o-nitrobenzaldehyde in CH2Cl2 (CD2Cl2), containing different amounts of water. The reaction kinetics was monitored by 1H and 13C NMR. The addition of water ...
Added: October 10, 2019
Kharitonov V., Evgeniya Podyacheva, Chusov D. et al., Organic Letters 2023 Vol. 25 No. 49 P. 8906-8911
A simple four-step route to a chiral tetrahydrofluorenyl rhodium catalyst from naturally occurring (−)-α-pinene was developed. Our approach does not use multistep and time-consuming procedures such as chiral HPLC or diastereomeric resolution. The key to success lies in the face-selective coordination of rhodium to the sterically hindered tetrahydrofluorenyl ligand, giving only one diastereomeric complex. This ...
Added: January 18, 2024
Bardonov D., Komarov P., Ovchinnikova V. et al., Organometallics 2021 Vol. 40 No. 9 P. 1235-1243
A series of mononuclear aryl-substituted cyclopentadienyl complexes [CpPh3LnCl2(Me3tach)] (Ln = Tb (4), Ln = Nd
(5)), [CpPh2ArTbCl2(Me3tach)] (6), and [CpPh3LnCl2(Me3tacn)] (Ln = Tb (7), Ln = Nd (8), CpPh3: 1,2,4-triphenylcyclopentadienyl, CpPh2Ar: 1,2-diphenyl-4-(o-methoxyphenyl)cyclopentadienyl, Me3tach: 1,3,5-trimethyl-1,3,5-triazacyclohexane, Me3tacn: 1,4,7-trimethyl-1,4,7-triazacyclononane) have been synthesized from polynuclear precursors, using cyclic tridentate nitrogen-based ligands to prevent formation of ate complexes. All the obtained complexes have been ...
Added: June 26, 2021
Chusov D., Yagafarov N., Muratov K. et al., European Journal of Organic Chemistry 2018 Vol. 2018 No. 4 P. 557-563
A catalytic system for the atom‐economical Ru‐catalyzed reductive amidation of aldehydes was developed. A cyclopentadienyl ruthenium catalyst was employed in this process with loadings as low as 0.5–1 mol‐%, and carbon monoxide was used as the deoxygenative agent. A number amides and aromatic aldehydes were able to successfully afford the corresponding secondary amide in yields ...
Added: June 26, 2019
Runikhina S., Afanasyev O., Kuchuk E. et al., Chemical Science 2023 Vol. 14 P. 4346-4350
Converter gas is a large scale waste product that is usually burned to carbon dioxide and contributes to the world emission of greenhouse gases. Herein we demonstrate that instead of burning the converter gas can be used as a reducing agent in organic reactions to produce valuable pharmaceuticals and agrochemicals. In particular, amide-based selected drug ...
Added: August 11, 2023
Лаврова М. А., Lunev A. M., Гончаренко В. Е. et al., Координационная химия 2022 Т. 48 № 6 С. 343-351
Новый комплекс [RuL(Dmdcbp)2]PF6 (I) получен последовательным взаимодействием [Ru-p-cymene]2Cl4 с 3,3',5,5'-тетраметил-1,1'-бифенил-4,4'-бипиразолом (L) и 4,4'-дикарбокси-2,2'-бипиридином в среде метанол–хлороформ. Состав комплекса I подтвержден методами ЯМР и элементным анализом, изучены оптические и люминесцентные свойства комплекса. Лиганд L впервые охарактеризован методом РСА (CIF file CCDC № 2118676). Для интерпретации спектров поглощения и испускания проведены квантово-химические расчеты в рамках теории функционала плотности. Комплекс ...
Added: October 17, 2022
Doronin S., Budkov Y., Itkis D., Carbon 2021 Vol. 175 P. 202-214
Based on the quantum-mechanical theory of electron transfer (ET), the parameter was proposed to describe the electrochemical activity of doped graphenes. The parameter is calculated using the density of states (DOS), local density of state (LDOS) values, which are in turn obtained from the density functional theory (DFT) calculations and reorganization energies of redox system. ...
Added: January 12, 2021
Заварзин С. В., Масленников А. Г., Гедгодв К. Н. et al., Радиохимия 2016 Т. 58 № 6 С. 506-511
The electrochemical properties of URu3 intermetallic compound (IMC) in 0.5–8 M HNO3 solutions were studied by linear voltammetry and galvanostatic electrolysis. In 0.5–2 M HNO3, URu3 occurs in the passive state at potentials lower than +1.3 V (here and hereinafter, vs. SHE), and in 4–8 M HNO3, an anodic oxidation peak is observed at potentials ...
Added: September 26, 2019
Kolos A., Nelyubina Y., Dmitry S. Perekalin, Organometallics 2022 Vol. 41 No. 21 P. 3038-3043
The parent ethylene rhodium(I) complex [(C2H4)2RhCl]2 reacts with internal alkynes to give binuclear metallacycles [(C4R4)Rh2Cl2(C2H4)]2 (R = Me, Et, CH2OMe, Ph), which can act as catalytic intermediates in cyclotrimerization reactions. These metallacycles can be converted into catalytically inert metallocenes CpRh(η5-C4R4RhCp) by addition of CpTl. Further reactions of these metallocenes with [CpRhI2]x and AgBF4 lead to ...
Added: January 24, 2023
Shapovalov S., Polyhedron 2018 Vol. 149 P. 73-78
Claisen condensation of acetylferrocene (eta(5)-C5H5)Fe(eta(5)-C5H4COCH3) and methyl ether of cymantrenecarboxylic acid (CO)(3)Mn(eta(5)-C5H(4)COOMe) results in beta-diketone (eta(5)-C5H5)Fe(eta(5)-C5H4)-C(O) CH2C(O)-(eta(5)-C5H4)Mn(CO)(3) (I) which reacts with hydrazine to form a heterometallic pyrazole (eta(5)-C5H5)Fe(eta(5)-C5H4)-N2C3H3-(eta(5)-C5H4)Mn(CO)(3) (II) or reacts with diiodo(p-cymene)ruthenium(II) dimer giving chelate beta-ketoenolate complexes of ruthenium, (p-cymene)RuI[eta(5)-C5H5)Fe(eta(5)-C5H4)-C(O)CHC(O)-(eta(5)-C5H4)Mn(CO)(3)] (III). The structures of complexes I-III were determined by single crystal X-ray diffraction. Electrochemical ...
Added: December 2, 2019
Shvydkiy N., Petrushina T., Dmitry S. Perekalin, ChemCatChem 2021 Vol. 13 No. 12 P. 2873-2878
Cyclobutadiene rhodium complexes [(C4R4)RhX]2 (R=Et, Ph; X = I, Cl) at 0.5 mol% loading catalyze the formation of aromatic amides from various indoles, tosyl azide, and carbon monoxide (1 atm). The reaction gives good yields of the target products (typically 60‐85%) and tolerates both donor and moderately acceptor substituents in the indoles (alkyl, OMe, Hal, ...
Added: January 24, 2023
Sedov I., Макарян И. А., Савченко В. И., Катализ в промышленности (перевод) 2023 Т. 23 № 4 С. 6-32
Представлен обзор, посвященный обобщению и сравнительному анализу литературных данных последних лет по исследованиям в области конверсии диоксида углерода в метанол, диметиловый эфир и углеводороды С2+, включая олефины, путем каталитического гидрирования. Показано, что основными путями достижения высокой активности и селективности таких процессов являются направленный дизайн катализаторов и подбор условий проведения процессов гидрирования, в том числе с ...
Added: February 28, 2024
Mandal R., Barsu N., Garai B. et al., Chemical Communications 2021 Vol. 57 No. 91 P. 12167-12170
A new protocol is developed for the mono- and bis-ortho-C–H alkynylation of easily accessible benzamide derivatives using alkynyl bromides at room temperature by merging cobalt and photocatalysts. The diverse reactivity of various alkynyl bromides towards the C–H alkynylation and competing C–H/N–H bond annulation reactions has been demonstrated to give the corresponding products in good yields ...
Added: January 24, 2023
Komarova A., Dmitry S. Perekalin, Organometallics 2023 Vol. 42 No. 13 P. 1433-1438
There is a common assumption that replacement of the classical catalyst based on rare and expensive noble metals by the catalysts based on earth-abundant metals will dramatically reduce the costs of organic synthesis. Herein we demonstrate that it may not be true, mainly because sophisticated organic substrates and modern reagents are often as expensive as ...
Added: August 11, 2023
Shvydkiy N., Rimskiy K., Dmitry S. Perekalin, Applied Organometallic Chemistry 2023 Vol. 37 No. 3 Article e7008
The readily available cyclobutadiene platinum complex [(C4Et4)PtCl2] catalyzes hydrosilylation of alkenes and alkynes. The reaction typically proceeds at room temperature and does not require any solvent. The target products are obtained from both terminal and internal alkynes, as well as from terminal alkenes in 43−99% yields. The scope of silanes includes various tertiary silanes (Et3SiH, ...
Added: January 24, 2023
Svitanko I., Стахеев А. Ю., Рассолов А. В. et al., Mendeleev Communications 2017 Vol. 27 No. 6 P. 615-617
The hydrogenation of diphenylacetylene (DPA) on palladium–silver catalysts with a single-atom structure was investigated. It has been shown experimentally that the reaction rate of alkene to alkane hydrogenation is substantially lower than the rate of DPA semi-hydrogenation. The kinetic barriers of all stages of hydrogenation were calculated by the DFT method. ...
Added: October 26, 2018
Kolos A., Nelyubina Y., Sundararaju B. et al., Organometallics 2021 Vol. 40 No. 22 P. 3712-3719
Herein we describe the synthesis and reactivity of rhodium catalysts with the very bulky cyclopentadienyl ligand C8H3tBu4 (designated as tBu4Cp). The reaction of [Rh(cod)Cl]2 with tert-butylacetylene in the presence of Et3N gives the complex (tBu4Cp)Rh(cod) (60–65% yield), in which the cyclopentadienyl ligand tBu4Cp is assembled from four alkyne molecules. The oxidation of (tBu4Cp)Rh(cod) with chlorine or bromine gives the corresponding ...
Added: January 24, 2023
Faraonov M., Romanenko N., Mikhailenko M. et al., New Journal of Chemistry 2021 Vol. 45 P. 13599-13607
Reduction of organic dye trans-perinone (its abbreviation is perinone) in different experimental conditions allows us to obtain and characterize radical anion {cryptand(K+)}[perinone˙−] (1) and dianion {PPN+}2[perinone2−]·2C6H4Cl2 (2) salts of this dye. The salts have layered structures. Perinone˙− radical anions form π–π stacked dimers in 1 with an effective interaction between them, whereas perinone2− dianions are ...
Added: October 21, 2022
Astakhov A., Chernenko A., Kutyrev V. et al., Inorganic Chemistry Frontiers 2023 Vol. 10 No. 1 P. 218-239
C-Amino-1,2,4-triazoles are challenging polynitrogen substrates for metal-catalyzed arylation due to their multidentate character, enhanced coordinating ability and decreased nucleophilicity of the amino group. In the present study, the Buchwald–Hartwig cross-coupling of diverse 3(5)-amino-1,2,4-triazoles with aryl chlorides and bromides delivering (hetero)arylamino-1,2,4-triazoles in good-to-excellent yields under Pd/NHC catalysis was developed. The use of Pd complexes with bulky ...
Added: February 14, 2024