Planar Chiral Rhodium Complex Based on the Tetrahydrofluorenyl Core for Enantioselective Catalysis

Kharitonov V.; Evgeniya Podyacheva; D. Chusov; Nelyubina Y.; Muratov D.; D. A. Loginov

doi:10.1021/acs.orglett.3c03726

Publications

?

Planar Chiral Rhodium Complex Based on the Tetrahydrofluorenyl Core for Enantioselective Catalysis

Organic Letters. 2023. Vol. 25. No. 49. P. 8906–8911.

Kharitonov V., Evgeniya Podyacheva, Chusov D., Nelyubina Y., Muratov D., Loginov D. A.

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 catalyst proved to be highly efficient for asymmetric C–H annulation of aryl hydroxamates with alkenes (yield up to 95%, 91% ee) at low loading (up to 0.4 mol % based on Rh).

Research target: Chemistry

Language: English

DOI

Keywords: rhodium complexes asymmetric catalysis C-H activation Homogeneous catalysis

Monometallic Ln3+ and heterometallic Ln3+–Cd2+ complexes based on pentafluorophenylacetic acid: efficient control of dimension and luminescent properties

Belousov Y., Кискин М. А., Sidoruk A. et al., Australian Journal of Chemistry 2022 Vol. 75 No. 9 P. 572–580

Four new complexes [Ln(pfaa)3(H2O)2]n (Ln = Eu (1), Tb (2)) and [Ln2Cd2(pfaa)10 (phen)2(EtOH)2]·2MeCN (Ln = Eu (3), Tb (4), phen = 1,10-phenanthroline) based on pentaphorphenylacetic acid (Hpfaa) have been prepared and completely investigated. The structures of compounds 1 and 3 were studied by single crystal X-ray diffraction analysis: the isostructural complexes 1 and 2 represent ...

Added: August 26, 2026

Understanding the electric double layer at electrode–electrolyte interfaces, Part III: crystallographic-face dependence of silver capacitance in aqueous NaF solutions

Mazur D., Brandyshev P., Doronin S. V. et al., Electrochimica Acta 2026 Vol. 577 Article 149729

The electric double layer (EDL) at a single-crystal metal surface is controlled not only by the electrolyte composition and the electrode potential, but also by the atomic structure of the surface itself. This makes the Ag(hkl)/NaF interface a stringent test for continuum theories of the EDL. In the third part of our series, we examine ...

Added: August 20, 2026

Hall effect in electrolyte solutions: Self-consistent Debye–Hückel–Onsager theory

Budkov Y., Kalikin N., Journal of Chemical Physics 2026 Vol. 165 Article 064506

A self-consistent statistical-mechanical theory of the Hall effect in electrolyte solutions is developed by extending the self-consistent Debye–Hückel–Onsager (SCDHO) framework to crossed electric and magnetic fields. The theory incorporates non-local ionic charge distributions via Slater-type form factors, regularizing the Coulomb interaction at short range, and accounts for dielectric friction through ion-specific coefficients, employing experimental values ...

Added: August 12, 2026

Charge-controlled binding, alloy synergy, and the copper anomaly in Au–Ag–Cu dimers to clusters: DFT-derived design rules for targeted drug delivery

Novikov A., New Journal of Chemistry 2026 Vol. 50 P. 13931–13957

The rational design of coinage metal nanocarriers requires a mechanistic understanding of metal-drug binding and predictive descriptors that translate molecular interactions into design rules. Using DFT (B3LYP-D3BJ/def2-TZVP, SMD water), we systematically investigated the binding of 5-fluorouracil (5-FU) and levodopa (l-DOPA) to neutral and cationic homo- and heteronuclear dimers of Au, Ag, and Cu (Au2, Ag2, ...

Added: August 12, 2026

Surface-sulfonated Al₂O₃, CeO₂, and TiO₂ as functional fillers for Nafion-type gel polymer electrolytes for lithium metal batteries

Voropaeva D., S. Novikova, I. Stenina et al., Solid State Ionics 2026 Vol. 445 Article 117288

Composite gel polymer electrolytes based on a perfluorinated sulfonic acid cation-exchange MF-4SC membrane containing surface-sulfonated nanoparticles of aluminum oxide, cerium (IV) oxide, and titanium oxide (sAl2O3, sCeO2, and sTiO2, respectively) were prepared by casting from a dispersion in N,N-dimethylformamide and plasticized with a 1,3-dioxolane/1,2-dimethoxyethane mixture. The influence of the filler nature on ionic conductivity, solvent uptake, activation energy, lithium ...

Added: July 30, 2026

Long-range machine-learning potentials with environment-dependent charges enable predicting LO-TO splitting and dielectric constants

Korogod D., Shapeev A., Ivan S. Novikov, Physical Review B: Condensed Matter and Materials Physics 2026 Vol. 114 No. 2 Article 024104

We present two models with explicit long-range electrostatics in the form of Coulomb interactions. Both models include point charges depending on their local atomic environments, and the second model also conserves a total charge of an atomic system. We combine the proposed long-range models with the local moment tensor potential (MTP) and demonstrate that they ...

Added: July 22, 2026

A Way to Create Mn-Containing GdFe3(BO3)4 and the Dopant Effect on Its Magnetic Properties

Moshkina E., Molokeev M., Zolotov A. et al., Journal of Alloys and Compounds 2026 Vol. 1077 Article 189412

A wide series of substitutions in a subsystem of small radii cations M = Al, Cr, Fe, Ga, Sc is possible in rare-earth borates ReM3(BO3)4 with the huntite structure. However, the existence of these compounds where M = Mn still raises doubts. The study presents a synthetic approach developed in the framework of the flux method allowing for the required ...

Added: June 29, 2026

Incorporating Scientific Knowledge into Neural Network Density Functionals

Schneider M., Zaripov D., Dokin R. et al., Journal of Chemical Theory and Computation 2026 Vol. 22 No. 9 P. 4405–4414

Density functional theory (DFT) is the workhorse of modern reactions and materials modeling. While the exact functional remains unknown, many approximations to it have been constructed either by hand-crafting functional forms to satisfy exact constraints or by machine learning. In this work, we show how both of these approaches can be fused to build both ...

Added: June 26, 2026

Electrodeposition and electrochromic properties of hydrated mixed oxides MoxW1-xO3·2H2O films

Laurinavichyute V., Levin E. E., Mironkova A. A. et al., Surfaces and Interfaces 2026 Vol. 81 Article 108389

In this work we characterize mixed Mo-W acidic deposition solutions with Mo content ranging from 0 to 100 mol.% by Raman and UV–Vis spectroscopy. The obtained distribution diagram of mixed isopolyanions allows one to explain the observed change in film deposition rate with increase in Mo content. It was found that the initial decrease in ...

Added: June 24, 2026

Impact of heat treatment on microstructure and mechanical properties of additively manufactured aluminum bronze

Filippova A. V., Yurchenko N. Y., Smirnov S. A. et al., Journal of Alloys and Compounds 2026 No. 1074 Article 189162

This study investigates the effects of post-processing heat treatment at 300–500 °C on the microstructure, hardness, and tensile properties of laser powder bed fusion (PBF-LB) processed Al-bronze processed with energy densities (ED) in the range of 125–938 J/mm3. In the as-printed state, sharp needle-like α + β′ laths form at lower ED whereas with increasing ED, the β′ ...

Added: June 12, 2026

DFT-guided charge-state engineering of gold clusters for levodopa recognition: fundamental principles for drug delivery applications

Obijiofor O., Novikov A., New Journal of Chemistry 2026 Vol. 50 No. 23 P. 9749–9768

Rational design of gold-based nanocarriers for neurotherapeutics requires atomic-scale understanding of drug-material interactions. Density functional theory calculations were performed to investigate levodopa (L-DOPA) adsorption on small gold clusters (Au2–Au4) with cationic, neutral, and anionic charges, with additional validation on a larger Au10 cluster using multiple low-energy isomers. Binding free energies (ΔGbind), charge transfer, and electronic descriptors ...

Added: June 3, 2026

Facile and Green Approach to Synthesize Biomass-Derived Zero-/Two-Dimensional Carbon Dots/g-C3N4 Heterojunction for Efficient Photocatalytic and Photoelectrocatalytic Applications

Das A., Saikia J., Maji N. et al., ChemNanoMat 2026 Vol. 12 No. 5 Article e202500733

Developing efficient photoactive materials from bio-derived resources is vital yet challenging for achieving effective water splitting performance. In this work, nano carbon dots (CDs) of zero-dimensional (0D) were synthesized from papaya peel through a simple and eco-friendly process and subsequently anchored onto the two-dimensional (2D) layered structure of graphitic carbon nitride (g-C3N4, GCN) at various ...

Added: June 2, 2026

Optimal Design of Copper-Doped ZnO Heterostructures for Photocatalytic and Photoeletrochemical Performance: A Combined Experimental and DFT Study

Wary R. R., Mahato B., Sharma N. et al., The Journal of Physical Chemistry Letters 2026 Vol. 17 No. 17 P. 5099–5107

Development of heterojunction materials is an efficient approach for enhancing photocatalytic and photoelectrochemical processes. We develop a ZnO/CuO heterojunction via Cu doping into a ZnO matrix. Structural characterization confirmed that Cu was effectively incorporated into ZnO without any structural changes. The improved optical properties and reduced charge carrier recombination of the doped samples were confirmed ...

Added: June 2, 2026

Synergistic Multimetal Effects in a High-Entropy Perovskite Oxide Anchored on Reduced Graphene Oxide for Accelerated Water Oxidation

Ostovari Moghaddam A., Mehrabi-Kalajahi S., Hossein Vasigh S. A. et al., The Journal of Physical Chemistry Letters 2026 Vol. 17 No. 13 P. 3978–3985

Water electrolysis is a key technology for sustainable energy conversion and hydrogen generation. Recently, high-entropy oxides (HEOs) have emerged as promising materials because they allow tuning of structural, electronic, and catalytic properties in multifunctional systems. Here, we report the synthesis of a multicomponent La(FeCoCuTiNiMnMgSnZn)O3 perovskite, and its hybridization with reduced graphene oxide (rGO) to form a ...

Added: June 1, 2026

Band Gap Renormalization Drives Ultrafast Charge Separation and Slow Recombination in Covalently Functionalized Carbon Nanotubes: Nonadiabatic Molecular Dynamics Simulation

Chowdhury U., Mondal S., Dey S. et al., Journal of the american chemical society 2026 Vol. 148 No. 23 P. 24538–24550

Covalent functionalization offers a versatile platform to engineer carbon nanotube properties for optoelectronics applications. We demonstrate by atomistic quantum dynamics simulation that covalent functionalization can renormalize the CNT band gap, split the degenerate CNT band edge states, and strongly influence charge carrier separation and recombination dynamics. Open-ring CNT functionalization (O-CNT) largely retains the π-conjugation, whereas ...

Added: June 1, 2026

An IQA/QTAIM Approach to the Chalcogen Bond

Jiménez-Grávalos F., Alexander S. Novikov, Pendás Á. M., Communications in Computational Chemistry 2026 Vol. 8 No. 2 P. 203–210

Chalcogen bonds (ChBs) are often interpreted as 𝜎-hole driven electrostatic interactions between a chalcogen atom and a Lewis base, yet their covalent character remains under active discussion. Here, we present a real-space, reference-free study of prototypical X2Ch···X– complexes (X = F, Cl; Ch = O, S) using the Interacting Quantum Atoms (IQA) energy decomposition within ...

Added: May 27, 2026

Singlet oxygen-mediated oxidation of sulfides with palladium(II) porphyrinates: The effect of partly conjugated peripheral substituents

Uskov F., Korobkov S., Birin K. P. et al., Journal of Photochemistry and Photobiology A: Chemistry 2026 Vol. 474 Article 116936

Oxidation of sulfides by singlet oxygen has been extensively studied, yet the structure-photoactivity relationship of these photosensitizers remains underinvestigated. In the present work the photocatalytic performance of a set of functionalized palladium(II) porphyrinates was comprehensively investigated in the photocatalytic oxidation of sulfides to reveal mutual influence of structural peculiarities onto the photosensitizing properties. The photophysical ...

Added: May 27, 2026

Rhodium Catalysts Based on Polyphenyl-Substituted Cp Ligands for Regioselective Annulation of Aryl Hydroxamates with Terminal Alkenes

Kharitonov V., Antonova A., Muratov D. et al., Organometallics 2025 Vol. 44 No. 19 P. 2301–2308

The readily available tetraphenylcyclopentadienyl rhodium complex [CpPh4RhCl2]2 effectively catalyzes the annulation of aryl hydroxamates with terminal alkenes to selectively form 4-substituted dihydroisoquinolones. The ligand volume has a crucial influence on the selectivity and efficiency of the reaction. The use of the overloaded pentaphenylcyclopentadienyl ligand CpPh5 or its less bulky pentabenzyl analog CpBn5 resulted in a dramatic decrease in ...

Added: February 20, 2026

Synthesis of chiral boranes via asymmetric insertion of carbenes into B–H bonds catalyzed by the rhodium(I) diene complex

Ankudinov N., Komarova A., Evgeniya S. Podyacheva et al., Chemical Communications 2024 Vol. 60 No. 65 P. 8601–8604

Molecules with chiral boron atoms have been scarcely studied due to limited synthetic access. Herein, we report a new method for their synthesis via asymmetric insertion of arydiazoacetates into the B–H bonds of prochiral carbene–boranes NHC–BH2R. The reaction is catalyzed by the rhodium(I) complex with the chiral diene ligand tBu2-TFB, which can be conveniently prepared by ...

Added: February 23, 2025

Synthesis of Isoquinoline-Containing 5,6-Dicyano-2,1,3-Benzothiadiazoles: Unusual Heterocyclization into Dibenzo-1,6-Naphthyridine Framework

Gribanov P., Vorobyeva D., Loginov D. A. et al., Asian Journal of Organic Chemistry 2024 Vol. 13 No. 9 Article e202400226

An efficient access to novel families of cyano-containing polyheteroaromatic D- A molecules with extended π-conjugation, including dibenzo[c,h][1,6]naphthyridine derivatives, has been elaborated. The synthetic strategy is based on the sequence of metal-catalyzed annulation and cross-coupling reactions starting from available 4-ethynyl-5,6-difluoro-7-(pmethoxyphenyl)- 2,1,3-benzothiadiazole to get a new series of isoquinoline-linked BTD-based D- A compounds, which further undergo a selective cyanation ...

Added: February 20, 2025

Rhodium Catalysts Based on Phenyl Substituted Cp Ligands for Indole Synthesis via Oxidative Coupling of Acetanilides and Alkynes

Kharitonov V., Muratov D., Rodionov A. et al., Advanced Synthesis and Catalysis 2024 Vol. 366 No. 22 P. 4729–4736

Rhodium-catalyzed oxidative coupling of acetanilides and alkynes via C􀀀 H activation is the most powerful synthetic tool for producing the indole motif from commercially available precursors. However, this reaction usually requires large catalyst loadings (5 mol% of rhodium). In this study, a 1,2-diphenylcyclopentadienyl ligand-based catalyst was developed that works well at 1 mol% loading of ...

Added: February 20, 2025

Planar-chiral arene ruthenium complexes: synthesis, separation of enantiomers, and application for catalytic C–H activation

Mikhail A. Boym, Pototskiy R., Evgeniya S. Podyacheva et al., Chemical Communications 2024 Vol. 60 No. 33 P. 4491–4494

Heating tert-butyl-tetraline with [(p-cymene)RuCl2]2 produces the racemic complex [(arene)RuCl2]2, which can be separated into enantiomers by chromatography of its diastereomeric adducts with chiral phosphine ligand. The resolved chiral complex catalyzes C–H activation of N-methoxy-benzamides and their annulation with N-vinyl-pivaloyl amide giving dihydroisoquinolones in 50–80% yields and with 40–80% enantiomeric excess. ...

Added: January 23, 2025

A synthetic route to artificial chiral α-amino acids featuring a 3,4-dihydroisoquinolone core through a Rh(iii)-catalyzed functionalization of allyl groups in chiral Ni(ii) complexes

Arsenov M., Stoletova N., Smol'yakov A. et al., Organic and Biomolecular Chemistry 2023 Vol. 21 No. 46 P. 9143–9149

Currently, non-proteinogenic α-amino acids (α-AAs) have attracted increasing interest in bio- and medicinal chemistry. In this context, the first protocol for the asymmetric synthesis of artificial α-AAs featuring a 3,4-dihydroisoquinolone core with two stereogenic centers was successfully elaborated. A straightforward Rh(III)-catalysed C–H activation/annulation reaction of various aryl hydroxamates with a set of robust and readily ...

Added: January 18, 2024

Tandem C–H Annulation Reaction of Benzaldehydes and Aminobenzoic Acids with Two Equivalents of Alkyne toward Isocoumarin-Conjugated Isoquinolinium Salts: A Family of Organic Luminophores

Arsenov M., Muratov D., Nelyubina Y. et al., Journal of Organic Chemistry 2023 Vol. 88 No. 13 P. 9360–9371

A novel rhodium-catalyzed tandem C–H annulation of commercially available benzaldehydes and aminobenzoic acids with 2 equiv of alkyne is reported for the construction of isocoumarin-conjugated isoquinolinium salts that demonstrate diverse outstanding photoactivity. Depending on the substituents in the isoquinolinium moiety, they display either highly efficient fluorescence (up to 99% of quantum yield) or strong fluorescence ...

Added: January 18, 2024