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Fluorinated Unsymmetrical N,N-Diaryl Imidazolium SaltsNew Functionalized NHC-Ligand Precursors
Chemistry - A European Journal. 2017. Vol. 23. No. 27. P. 6663–6674.
An efficient and scaled-up synthesis of the imidazol-2-ylidene-based unsymmetrical NHC precursors bearing the sterically demanding hexafluoroisopropylalkoxy group [(CF3)(2)(OR)C-] at the ortho position of the N-aryl substituent was developed. The key step of the method involved the transformation of a Mes-substituted oxazolinium tetrafluoroborate salt through the reaction with the corresponding binucleophilic fluoroalkyl-substituted aniline. The subsequent post-modification of the resulting hydroxyl-containing salt through a simple one-step O-alkylation protocol provided access to a new family of unsymmetrical fluorinated NHC precursors. These compounds were successfully utilized for the preparation of several novel metal complexes. The molecular structures of some NHC precursors and their metal complexes have been unambiguously characterized by single-crystal X-ray diffraction analysis. A preliminary evaluation of the catalytic activity of the palladium complexes was performed on a Buchwald-Hartwig amination reaction. As a result, two PEPPSI-type (PEPPSI=pyridine-enhanced pre-catalyst preparation stabilization and initiation) Pd complexes have demonstrated promising activity in alkane solvents.
Kolos A., Nelyubina Y., Godovikova M. et al., Chemistry - A European Journal 2025 Vol. 31 No. 41 Article e202501793
Cyclopentadienyl rhodium complexes (C5R5)RhLx are widely used as homogeneous catalysts. Herein we report the synthesis of such complexes with structurally diverse cyclopentadienyl ligands in one step directly from alkynes. Specifically, reactions of bulky terminal alkynes (tert-butylacetylene or trimethylsilylacetylene) with activated internal alkynes (ethyl 2-butynoate or dimethyl acetylenedicarboxylate (DMAD)) and [(cod)RhCl]2 produce either cyclopentadienyl or pentalene-type ...
Added: February 15, 2026
Ankudinov N., Alexeev N., Podyacheva E. et al., Chemical Science 2025 Vol. 16 No. 15 P. 6298–6306
Organic compounds with boron–nitrogen bonds are widely used as fluorescent sensors and semiconducting materials. This paper presents a new approach for the formation of B–N bonds via catalytic insertion of nitrenes into B–H bonds. The reaction proceeds most selectively for cyclic boranes with a 2-phenylpyridine framework and nitrenes generated in situ by the oxidation of ...
Added: February 15, 2026
Tsygankov A., Kozlov A., Liao S. et al., Coordination Chemistry Reviews 2024 Vol. 519 Article 216114
Transition metal (TM)-based catalysts are indispensable tools in modern organic synthesis. Although many efficient catalysts based on TMs are already known, further improvement of catalytic system activity remains one of the major goals of transition metal coordination chemistry. A large number of TM-based catalysts contain halide ligands, mostly chlorides and bromides. Transition metal fluorides have ...
Added: January 23, 2025
Jiang X., Tan J., Liu D. et al., The Journal of Physical Chemistry Letters 2024 Vol. 15 No. 13 P. 3611–3618
Further improving the activity and selectivity of photocatalytic CO2 reduction remains a challenge. Herein, we propose a new strategy for synergistically promoting photocatalytic CO2 reduction by combining two-dimensional (2D) ferroelectric polarization and single-atom catalysis. Our calculations showed that the ferroelectric polarization of CuBiP2Se6 provides the internal driving force for the separation and migration of photogenerated carriers, which provides ...
Added: April 11, 2024
Petrova V., Domnin A., Porozov Yuri et al., Journal of Computational Chemistry 2024 Vol. 45 No. 3 P. 170–182
Prediction of catalytic reaction efficiency is one of the most intriguing and challenging applications of machine learning (ML) algorithms in chemistry. In this study, we demonstrated a strategy for utilizing ML protocols applied to Quantum Theory of Atoms In Molecules (QTAIM) parameters to predict the ability of the A17 L47K catalytic antibody to covalently capture ...
Added: January 29, 2024
Lukin R., Grigoriev R., Yarullin A. et al., , in: Proceedings of the NeurIPS 2021 Competitions and Demonstrations Track.: PMLR, 2022. P. 1–12.
In this report, we describe the Open Catalyst Challenge held at NeurIPS 2021, focusing on using machine learning (ML) to accelerate the search for low-cost catalysts that can drive reactions converting renewable energy to storable forms. Specifically, the challenge required participants to develop ML approaches for relaxed energy prediction, i.e. given atomic positions for an ...
Added: January 12, 2024
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
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
Voronin A., Sofya P. Balabanova, Fedyanin I. et al., Molecules 2022 Vol. 27 No. 19 Article 6287
A strategy for the synthesis of 5-((2-cyanoethyl)-X-amino)-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazol-5-ium-4-ides (X = H; CH2CH2CN; NO2 (4a); CN (4b); CO2Et (4c)) starting from 3-amino-4-azido-1,2,5-oxadiazole was developed. The key step in this strategy is the intramolecular thermolytic cyclization of the azido group and the bis(2-cyanoethyl)triazene group. Removal of the 2-cyanoethyl protecting group from amides 4a–c gave potassium salt of the corresponding nitramide and ...
Added: January 31, 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
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
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
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
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
Cha J., Lee E., Dmitry V. Yandulov, Inorganic Chemistry 2022 Vol. 61 No. 37 P. 14544–14552
Molecular oxygen (O2) remains to be an ideal yet underutilized feedstock for the oxidative transformation of organic substrates and renewable energy systems such as fuel cells. Palladium (Pd) has shown particular promise in enabling these applications. The present study describes a Pd-mediated O2 reduction to water via C–H activation of 9,10-dihydroanthracene (DHA) by a Pd(II) ...
Added: October 24, 2022
Lee E., Lee J., Yandulov D. V., European Journal of Inorganic Chemistry 2017 Vol. 2017 P. 2058–2067
Added: October 24, 2022
Lee E., Bae D. Y., Yandulov D. V., Bulletin of the Korean Chemical Society 2016 Vol. 37 P. 1745–1746
Added: October 24, 2022
Lee E., Bae D. Y., Park S. et al., European Journal of Inorganic Chemistry 2016 Vol. 2016 P. 4561–4564
Added: October 24, 2022
A. B. Yaroslavtsev, I. V. Svitanko, Egorov M. P., Russian Chemical Bulletin 2022 Vol. 71 No. 1 P. 176–180
Probably, humans are called Homo sapiens because they learn something throughout the whole life. As soon as we are born, we begin to be aware of the surrounding world bit by bit, then we go to school, to the institute, and to post-graduate courses. However, it is important that, having reached a certain level, a ...
Added: October 18, 2022
Shirokova V., Smirnov A., Zaitseva E. et al., Chemistry Of Heterocyclic Compounds 2022 Vol. 58 P. 255–259
Added: June 19, 2022
Ivanov D., Zaitseva E., Smirnov A. et al., Advanced Synthesis and Catalysis 2022 Vol. 364 No. 9 P. 1587–1595
Added: June 19, 2022
Larin A., Shaferov A., Kulikov A. et al., Chemistry - A European Journal 2021 Vol. 27 P. 14628–14637
cA series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by ...
Added: October 13, 2021