Article
Multidisciplinary Sciences
Geun Seok Lee, Beomsoon Park, Soon Hyeok Hong
Summary: In this study, an efficient method for the stereoretentive direct cross-coupling of chiral amino acid chlorides and unactivated C(sp(3))-H hydrocarbons was achieved via photoredox catalysis. The strategic generation of an N-acyllutidinium intermediate facilitated the synthesis of chiral amino ketones with retention of stereochemistry.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Vivek Gupta, Sadhana Singh, Sharad Kumar Sachan, BrijKishor Maurya, Subhamoy Char, Dasari L. V. K. Prasad, Ganapathi Anantharaman
Summary: This study investigates the reaction properties and products of acyclic palladium amidine chloride under different conditions. It is found that cyclic six-membered (triazapentadiene)palladium complexes can be obtained by reacting palladium complexes or formamidinium salts with acetonitrile, but different products are obtained with acetonitrile or acrylonitrile.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Rashid G. Siddique, Jacob J. Whittaker, Hydar A. AL-Fayaad, John C. McMurtrie, Jack K. Clegg
Summary: Despite the use of achiral ligands, metallosupramolecular assemblies containing octahedral metal centers exhibit strong stereochemical communication between the metal centers, resulting in the formation of homochiral assemblies.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Rashid G. Siddique, Jacob J. Whittaker, Hydar A. AL-Fayaad, John C. McMurtrie, Jack K. Clegg
Summary: Despite the use of achiral ligands, there is still strong stereochemical communication observed in most metallosupramolecular assemblies with octahedral tris-bidentate metal centers, resulting in the formation of homochiral assemblies. In this study, it is found that even when resolved stereocenters are attached to the central part of a quaterpyridine ligand, the stereochemical coupling is not enough to disrupt the strong stereochemical communication between metal centers.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Ting-Feng Wu, Yue-Jiao Zhang, Yue Fu, Fang-Jie Liu, Jian-Tao Tang, Peng Liu, F. Dean Toste, Baihua Ye
Summary: Transition metal-catalyzed cross-electrophile coupling (XEC) is a powerful method for constructing C(sp(2))-C(sp(2)) bonds in biaryl molecules from abundant aromatic halides. While the synthesis of unsymmetrical biaryl compounds through multimetallic XEC is valuable, the selective XEC of two heteroaromatic halides is still challenging. This study presents a homogeneous XEC method using a zirconaaziridine complex as a shuttle for dual palladium-catalyzed processes, offering opportunities for the development of transition metal reductive coupling catalysis.
Article
Chemistry, Multidisciplinary
Mo Chen, Austin M. Ventura, Soumik Das, Ammar F. Ibrahim, Paul M. Zimmerman, John Montgomery
Summary: Current methodologies for metal-catalyzed cross-couplings require the installation of reactive functional groups on both reaction partners in advance. In contrast, C-H functionalization approaches show potential in simplifying the substrates required; however, challenges such as low reactivity and similar reactivity of different C-H bonds add complexity. This study describes an oxidative cross dehydrogenative coupling of α-amino C(sp(3))-H bonds and aldehydes to produce ketone derivatives using an unusual reaction medium that simultaneously utilizes di-tert-butyl peroxide as an oxidant and zinc metal as a reductant. The method has a broad substrate scope and offers an attractive approach for accessing α-amino ketones through the formal acylation of C-H bonds adjacent to nitrogen in N-heterocycles. Experimental investigation and computational modeling provide evidence for a mechanistic pathway involving cross-selective nickel-mediated cross-coupling of α-amino radicals and acyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Connor P. Delaney, Eva Lin, Qinan Huang, Isaac F. Yu, Guodong Rao, Lizhi Tao, Ana Jed, Serena M. Fantasia, Kurt A. Puentener, R. David Britt, John F. Hartwig
Summary: Copper complexes catalyze cross-coupling reactions through a newly discovered mechanism. The copper(II) complexes catalyze Ullmann coupling by synthesizing the C-O bond through concerted oxidative addition. This mechanism allows for high turnover numbers and the reactions can be performed in air.
Article
Chemistry, Multidisciplinary
L. Reginald Mills, Racquel K. Edjoc, Sophie A. L. Rousseaux
Summary: New ligands are designed to exploit the reactivity of nitrile-containing additives in Ni catalysis for cross-coupling reactions involving tertiary nucleophiles. Kinetic and Hammett studies elucidate the role of the optimized ligand, promoting reductive elimination and stabilizing low-valent Ni. This study enables the synthesis of quaternary alpha-arylnitriles from disubstituted malononitriles through decyanation-metalation and Ni-catalyzed arylation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Raymond F. Turro, Julie L. H. Wahlman, Z. Jaron Tong, Xiahe Chen, Miao Yang, Emily P. Chen, Xin Hong, Ryan G. Hadt, K. N. Houk, Yun-Fang Yang, Sarah E. Reisman
Summary: Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of N-hydroxyphthalimide (NHP) esters and benzylic chlorides were conducted. The study revealed divergent mechanisms for these related transformations, with the mechanism of C(sp(3)) activation changing depending on the reactants used. Kinetic experiments showed that the rate of NHP ester reduction can be tuned by changing the Lewis acid. Spectroscopic studies and DFT calculations provided insights into the catalyst resting state and the origin of enantioinduction for the Ni-BOX catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Caleb E. Griesbach, Jean-Nicolas Desrosiers, Liam Sharninghausen, Teresa Makowski, Steven M. Guinness, Ethan Wood, Chase Salazar, Caleb Kong, Jenson Verghese
Summary: In this study, a Ni-catalyzed cross-coupling is used as a reversed strategy for the homogeneous deprotection of benzyl ethers, achieving the desired (hetero)aromatic alcohols containing heterocycles, alkenes, and ethers within 1 h by accelerating the reaction in batch using microwave heating or in flow using superheating in a plug flow reactor. This work highlights an alternative debenzylation strategy in flow for cases where hydrogenation using heterogeneous catalysts is not a viable option.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Organic
Anastasia A. Fesenko, Mikhail S. Grigoriev, Vladimir B. Arion, Anatoly D. Shutalev
Summary: The unprecedented self-assembly of novel 14-membered cyclic bis-thiosemicarbazone or/and 28-membered cyclic tetrakis-thiosemicarbazone upon acid-promoted cyclooligomerization of 4-(4-thiosemicarbazido)butan-2-one hydrazone has been discovered. By studying the influence of various factors, the optimal conditions for the highly selective formation of each macrocycle have been determined, leading to excellent yields. Plausible pathways for macrocyclizations have been discussed. The macrocycle precursor was prepared by the reaction of readily available 4-isothiocyanatobutan-2-one with an excess of hydrazine.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Robert Wethman, Joseph Derosa, Van T. Tran, Taeho Kang, Omar Apolinar, Anuji Abraham, Roman Kleinmans, Steven R. Wisniewski, John R. Coombs, Keary M. Engle
Summary: This study investigated the decomposition of primary sodium alkoxide salts under ambient storage conditions and its effects on commonly employed transition-metal-catalyzed cross-coupling reactions. Characterization of the main inorganic degradants was done using NMR, IR, and Raman spectroscopy, and it was found that CO2 in the air played a critical role in the decomposition process. The effects of storage conditions on decomposition were assessed, and preliminary experiments were conducted to understand the kinetics of this process.
Article
Chemistry, Multidisciplinary
David J. Charboneau, Haotian Huang, Emily L. Barth, Cameron C. Germe, Nilay Hazari, Brandon Q. Mercado, Mycah R. Uehling, Susan L. Zultanski
Summary: A series of new tunable homogeneous organic reductants based on a tetraaminoethylene scaffold have been synthesized, which exhibit enhanced air stability and solid state properties at room temperature. These reductants show significantly milder reduction potential than conventional reductants, allowing for controlled alkyl radical generation in Ni-catalyzed XEC reactions. The new reductants are expected to replace current homogeneous reductants due to their stability and lead to the development of novel synthetic methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Mahdi Keyhaniyan, Amir Khojastehnezhad, Hossein Eshghi, Ali Shiri
Summary: An efficient procedure was reported to prepare Fe3O4@SiO2 magnetic nanoparticles (MNPs) with immobilized nickel NPs for the synthesis of biaryl derivatives via the Suzuki-Miyaura cross-coupling reaction. The catalyst showed high activity and could be recovered and reused with no loss of activity over multiple runs.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Olga Kataeva, Kamil Ivshin, Kirill Metlushka, Kristina Nikitina, Vera Khrizanforova, Yulia Budnikova, Robert R. Fayzullin, Shamil Latypov, Sandra Schiemenz, Michael Bretschneider, Alexey Popov, Stanislav Avdoshenko, Yulia Krupskaya, Bernd Buchner, Martin Knupfer
Summary: A series of new charge-transfer cocrystals of F(2)TCNQ with anthracene, tetracene, and chrysene were prepared and characterized. The study revealed that face-to-face pi-pi interactions are crucial for the formation of cocrystals, but lateral noncovalent interactions also play a significant role in the supramolecular arrangement and charge transfer. UV/vis spectroscopy and electronic structure quantum chemical calculations classified these cocrystals as small-gap semiconductors with energy gaps of 0.7-1.3 eV.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Organic
Scott T. Shreiber, Gabriella I. Puchall, David A. Vicic
Summary: The homoleptic trifluoromethyl nickel complex catalyzes a stereoselective trifluoromethylation of brucine, leading to a trifluoromethylated derivative. The reaction also involves the isomerization of its alkenyl double bond, and a minor difunctionalization product is detected, suggesting a parallel radical addition process. Stoichiometric reactions between the nickel(II) catalyst precursor and brucine show no reactivity, but a reaction with a high-valent nickel(IV) complex results in the formation of trifluoromethylated derivative.
TETRAHEDRON LETTERS
(2022)
Article
Electrochemistry
Tatyana V. Gryaznova, Elizaveta O. Nikanshina, Robert R. Fayzullin, Daut R. Islamov, Maxim V. Tarasov, Kirill V. Kholin, Yulia H. Budnikova
Summary: A mild and efficient electrochemical method has been developed for the site-selective direct C(sp(2))-H phosphonation of acridine using triorganyl phosphites. The reaction proceeds without the need for catalysts, external oxidants, or metals, and leads to selective C9-phosphorylation in good yields. The mechanism of the reaction was investigated using voltammetry and EPR spectroscopy, and the intermediates were isolated and characterized using various techniques. This study provides insights into the reaction pathways, enabling the synthesis of phosphorylated acridine derivatives.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Teng Xue, Scott T. Shreiber, Roger E. Cramer, David A. Vicic
Summary: In this study, solvent-coordinated perfluoroethyl and n-perfluoropropyl cobalt complexes were synthesized and characterized. The electrochemical analysis revealed that [(MeCN)(4)Co(C2F5)(2)][PF6] is more easily reduced compared to [(MeCN)(3)Co (C2F5)(3)], which has significant implications for the development of redox-triggered reactions involving cobalt(II) intermediates.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kamil A. Ivshin, Kirill Metlushka, Anton Fedonin, Shamil K. Latypov, Vera V. Khrizanforova, Yulia H. Budnikova, Alexander E. Vandyukov, Airat G. Kiiamov, Artem Laskin, Stanislav M. Avdoshenko, Martin Knupfer, Olga Kataeva
Summary: A series of charge transfer cocrystals composed of methyl substituted anthracenes (MeAnt or Me2Ant) and FxTCNQ (x = 0, 1, 2) were synthesized. The crystal packing is influenced by various interactions, including pi-pi, F center dot center dot center dot H, N center dot center dot center dot H, and F center dot center dot center dot F interactions, as well as the steric effect of the methyl substituents. The introduction of methyl groups into the donor molecules promotes a skewed overlap mode, dipole-dipole interactions, and a three-dimensional network of intermolecular interactions.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Biochemistry & Molecular Biology
Maxim V. V. Tarasov, Olga D. D. Bochkova, Tatyana V. V. Gryaznova, Asiya R. R. Mustafina, Yulia H. H. Budnikova
Summary: This study describes an efficient electrochemical phosphorylation reaction of phenylacetylene controlled by non-noble-metal-based catalytic nanoparticles. The desired products are synthesized using a simple protocol at room temperature, utilizing silica nanoparticles loaded with one or two d-metal ions as nanocatalysts. The redox and catalytic properties of the silica nanoparticles can be adjusted by various parameters, such as the composition of the bimetallic systems, preparation method, and morphology. Monometallic silica nanoparticles enable phosphorylation of acetylene while retaining the triple bond, while bimetallic silica nanoparticles yield a bis-phosphorylation product. This is the first example of a regenerable and recyclable catalyst for the C-H/P-H coupling of acetylene and phosphine oxide.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Vera V. Khrizanforova, Robert R. Fayzullin, Tatiana P. Gerasimova, Mikhail N. Khrizanforov, Almaz A. Zagidullin, Daut R. Islamov, Anton N. Lukoyanov, Yulia H. Budnikova
Summary: The redox properties of monoiminoacenaphthenes (MIANs) were investigated using various electrochemical techniques. The obtained potential values were used to calculate the electrochemical gap and frontier orbital difference energy. The reduction of MIANs at the first peak potential was carried out, yielding two-electron one-proton addition products through controlled potential electrolysis. The structures of three new sodium complexes, three electrochemical reduction products, and one NaBH4 reduction product were determined by single-crystal X-ray diffraction.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Review
Electrochemistry
Yulia H. Budnikova, Egor L. Dolengovski, Maxim V. Tarasov, Tatyana V. Gryaznova
Summary: Advancements in electro-organic synthesis are driven by the search for innovative synthetic approaches, particularly in synthesizing and functionalizing complex molecules for medicinal chemistry. This also includes the importance of minimizing waste and ensuring energy efficient chemical transformations for future industrial processes. Organic chemistry offers limitless possibilities in performing chemical reactions, identifying complex processes, and generating active reagents. Electrochemistry allows for control over process selectivity through electrode potential and can oxidize/reduce low-reactive molecules while fine-tuning functional group conversions. Integrating organic electrosynthesis with other process techniques, such as flow chemistry, can enhance efficiency and sustainability.
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Egor L. Dolengovski, Tatyana V. Gryaznova, Yulia B. Dudkina, Daut R. Islamov, Robert R. Fayzullin, Oleg G. Sinyashin, Yulia H. Budnikova
Summary: The mechanistic details of the oxidative coupling of compounds with different redox centers were investigated using N-(quinolin-8-yl)-benzamide (L) as a model substrate. By controlling the chemical or electrooxidation parameters, different regioselective oxidative coupling products were obtained. The operative mechanism depends on the type of oxidized reaction center and the oxidant nature. The intermediate Co(II)[L-H]2 complex and C-H-activated CoIII metallacycle were isolated and characterized.
Article
Chemistry, Organic
Vera V. Khrizanforova, Robert R. Fayzullin, Yulia H. Budnikova
Summary: A heteroleptic binuclear manganese complex was synthesized and analyzed using single-crystal X-ray diffraction. Manganese ions show distinct geometries in the resulting complex, coordinating with the target product and a by-product of the condensation reaction between 2-picolylamine and acenaphthenequinone.
Article
Electrochemistry
Yulia H. Budnikova, Yulia B. Dudkina, Alexey A. Kalinin, Guzel M. Fazleeva, Liliya N. Islamova, Alina I. Levitskaya, Olga D. Fominykh, Marina Yu. Balakina
Summary: Electrochemical data was used to characterize chromophores with different donors, acceptors, and pi-bridges. A good correlation was found between electrochemical, optical, and calculated characteristics. Polyene pi-bridges provide better charge transfer ability and high sensitivity to the nature of the donor and acceptor. Indolizine donors produce chromophores with high first hyperpolarizability. The correlation between beta and 1/(Delta E-el)(2) is nearly linear.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Egor L. Dolengovski, Tatyana V. Gryaznova, Oleg G. Sinyashin, Elena L. Gavrilova, Kirill V. Kholin, Yulia H. Budnikova
Summary: An electrochemical reaction using Cu(OAc)(2) as a catalyst was developed to synthesize 4- or 2-aminoquinoline N-oxides with good yields. The reaction has mild conditions, room temperature operation, and the ability to control the process, making it a simple method for introducing morpholine substituent important in medicinal chemistry and other fields.
Article
Chemistry, Inorganic & Nuclear
Vera V. V. Khrizanforova, Robert R. R. Fayzullin, Artem S. S. Bogomyakov, Vladimir I. I. Morozov, Ruslan G. G. Batulin, Tatiana P. P. Gerasimova, Daut R. R. Islamov, Yulia H. H. Budnikova
Summary: A new bifunctional N-4-ligand was synthesized, and its structure and redox properties were investigated. The ligand was prepared in an anion-radical form via chemical and electrochemical reduction methods. New cobalt complexes with the ligand were obtained and characterized. The structures of the cobalt complexes were studied using X-ray diffraction, and their magnetic and electron paramagnetic resonance properties were analyzed. The results showed different coordination modes of the cobalt atom with the ligand.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Olga Bochkova, Svetlana Fedorenko, Artem Mikhailov, Gennadiy Kostin, Maxim Mikhailov, Maxim Sokolov, Julia Elistratova, Kirill Kholin, Maxim Tarasov, Yulia Budnikova, Guzel Sibgatullina, Dmitry Samigullin, Irek Nizameev, Vadim Salnikov, Ivan Yakovlev, Darina Rozhentsova, Anna Lyubina
Summary: This study reports the synthesis of silica nanoparticles incorporated with two photoactive components, which exhibit both synergistic and anti-synergistic effects. The amino-group modification on the surface of the nanoparticles facilitates the deposition of cluster units, resulting in heterometallic core-shell nanoparticles. The protein corona formed on the surface of these nanoparticles promotes high colloidal stability and efficient cellular internalization. Cytotoxicity measurements demonstrate the synergistic effect of the nanoparticles in dark conditions and the anti-synergistic effect in photo-induced cytotoxicity.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Scott T. Shreiber, Fatema Amin, Sascha A. Schafer, Roger E. Cramer, Axel Klein, David A. Vicic
Summary: A series of new anionic nickelate complexes were synthesized and characterized, and their electrochemical properties were studied. The results showed that the complexes exhibited different oxidation-reduction behaviors, and the NHC ligand environment played an important role in the release of trifluoromethyl and perfluoroalkyl radicals.
DALTON TRANSACTIONS
(2022)
