Article
Chemistry, Inorganic & Nuclear
Chaofan Sun, Ju-You Lu, Jian Lu
Summary: Efficient Pd-catalyzed regioselective B(6)-H phosphorization of nido-carboranes via cascade deboronation/B-H activation with various phosphines using 3-methylpyridine or isoquinoline as a directing group in combination with pyridine ligands has been developed, affording unprecedented B(6)-phosphinated nido-carborane derivatives with high selectivity in a simple one-pot process.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Sourav Kar, Subhash Bairagi, Jean-Francois Halet, Sundargopal Ghosh
Summary: Although Lipscomb predicted in 1977 that supra-icosahedral boron clusters would be viable, their synthesis has been hindered by the lack of suitable synthetic methodologies. This study reports the first examples of open 16-vertex oblato-hypotitanaborane clusters [(Cp*Ti)(2)B14H17R] (1: R = H; 2: R = Me) with a non-Wadean 19-skeletal-electron-pair count. Interestingly, these clusters exhibit a six-membered [Ti2B4] open face, which could potentially lead to the formation of closo-19-vertex clusters.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Krzysztof Fink, Mariusz Uchman
Summary: Boron cluster compounds are inorganic compounds with unique structures and properties that show promising antimicrobial activity and low sensitivity to pathogen resistance mechanisms. Their derivatives are effective against both standard and multi-drug resistant strains of pathogens.
COORDINATION CHEMISTRY REVIEWS
(2021)
Review
Chemistry, Medicinal
Guoqing Fang, Hongjuan Chen, Zhiyun Cheng, Zilong Tang, Yichao Wan
Summary: Heterocycles, especially azaindole derivatives, have become important sources of kinase inhibitors for drug design, due to their ability to form hydrogen bonds in ATP-binding sites. This review focuses on the recent development of azaindole derivatives as potential kinase inhibitors, targeting various kinases such as AAK1, ALK, AXL, Cdc7, CDKs, DYRK1A, FGFR4, PI3K, and PIM kinases. The structure-activity relationships and binding modes of these derivatives are also elucidated. This review provides insights for medicinal chemists in the rational design of more potent kinase inhibitors with the azaindole scaffold.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Fangxiang Sun, Shuaimin Tan, Hou-Ji Cao, Jingkai Xu, Vladimir I. Bregadze, Deshuang Tu, Changsheng Lu, Hong Yan
Summary: This research proposes a new molecular design strategy for achieving AIE properties by combining three-dimensional aromatic boron clusters of carboranes with vinyl group(s). A efficient synthesis method for boron cluster-based AIEgens is developed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Meng Chen, Jingkai Xu, Deshi Zhao, Fangxiang Sun, Songlin Tian, Deshuang Tu, Changsheng Lu, Hong Yan
Summary: This study presents a photocatalytic B-C coupling reaction for the selective functionalization of carboranes. The reaction involves the photo-induced decarboxylation of carborane carboxylic acids and generates boron vertex-centered carboranyl radicals. The reaction can be conducted under mild conditions and allows the synthesis of various functionalized carboranes, including a highly efficient blue emitter and a drug candidate for boron neutron capture therapy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Medicinal
Yichao Wan, Guoqing Fang, Hongjuan Chen, Xu Deng, Zilong Tang
Summary: This review summarizes recent advances of sulfonamide derivatives as potential anti-cancer agents, focusing on their applications on anti-cancer targets and corresponding structure-activity relationships.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Manjur O. Akram, John R. Tidwell, Jason L. Dutton, Caleb D. Martin
Summary: The synthesis of a single site neutral Lewis superacid, tris(ortho-carboranyl)borane (BoCb(3)), was achieved in one pot from commercially available materials. It was confirmed to be a Lewis superacid due to its high fluoride ion affinity (FIA), and exhibited stronger Lewis acidity compared to widely used fluorinated aryl boranes, as evidenced by the Gutmann-Beckett method and adducts with Lewis bases. The unusually high Lewis acidity can be rationalized by the electron-withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO. Catalytic studies demonstrated that BoCb(3) is a superior catalyst for promoting C-F bond functionalization reactions compared to tris(pentafluorophenyl)borane [B(C6F5)(3)].
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Jordi Poater, Clara Vinas, Miquel Sola, Francesc Teixidor
Summary: This study investigates the possibility of 3D/2D aromatic fusions and their relationship to electronic delocalization. While 2D/2D and 3D/3D aromatic fusions have been synthesized, the ineffective overlap between the pi-MOs of planar species and the n + 1 molecular orbitals in the aromatic cage makes 3D/2D aromatic combination impossible.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Zhen-Hua Wang, Tong Zhang, Qing-Fei Yan, Jian-Qiang Zhao, Yong You, Yan-Ping Zhang, Jun-Qing Yin, Wei-Cheng Yuan
Summary: In this article, various α-aryl vinylsulfonium salts were successfully transformed under mild reaction conditions, leading to the synthesis of diverse 1,2-dihydroquinoline and ring-fused tetrahydroquinoline skeletons with moderate to excellent yields. The potential application of the method was demonstrated by scale-up experiments and further derivatizations of the products. The developed protocol offers mild and transition-metal-free reaction conditions, along with easy operation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Multidisciplinary Sciences
Tobias Hartwig Bunning, Luigi Panza, Abdel Kareem Azab, Barbara Muz, Silvia Fallarini, Daniela Imperio
Summary: Boron Neutron Capture Therapy (BNCT) shows promise in treating non-curable cancers, with a new boron compound being discovered to selectively accumulate in tumor tissue. Hypoxia poses a challenge in cancer treatment, but a new compound exhibits toxicity in multiple myeloma cells and consistent intracellular boron accumulation.
Article
Chemistry, Multidisciplinary
Martin Hejda, Daniel Duvinage, Enno Lork, Antonin Lycka, Zdenck Cernosek, Jan Machacek, Sergey Makarov, Sergey Ketkov, Stefan Mebs, Libor Dostal, Jens Beckmann
Summary: The aryltellurenyl cation and the weakly coordinating carborane anion form an isolable ion pair complex, in which the Bronsted acidity of the formally hydridic B-H bonds is dramatically increased, leading to a proton transfer reaction at slightly elevated temperatures. The isolation of zwitterionic isomers further confirms the electrophilic activation of B-H bonds in the carborane moiety.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Crystallography
Albert Ferrer-Ugalde, Arantzazu Gonzalez-Campo, Jose Giner Planas, Clara Vinas, Francesc Teixidor, Isabel M. Saez, Rosario Nunez
Summary: A new set of mesomorphic materials is described, in which o-carborane clusters are covalently bonded to cholesteryl benzoate moieties through a designed linker. Compounds M2 and M3 exhibit chiral nematic phases, with M3 also displaying a blue phase, while M4 does not show liquid crystal behavior.
Article
Chemistry, Inorganic & Nuclear
Meghamala Sarkar, Evamarie Hey-Hawkins, Ramamoorthy Boomishankar
Summary: The encapsulation of icosahedral closo-dicarbadodecaborane (o-, m-, and p-carboranes) as guest molecules in the three isostructural tetrahedral cages [{Pd3(NiPr3)PO}4(Cl-AN)6] (1), [{Pd3(NiPr)3PO}4(Br-AN)6] (2), and [{Pd3(NiPr)3PO}4(H-AN)6] (3) was investigated. The formation of definite host-guest assemblies was confirmed by mass spectrometry, IR, and NMR spectroscopy. Diffusion coefficient measurements and hydrodynamic radius calculations suggested that the carborane isomers were encapsulated inside the cage assemblies. Energy optimization studies indicated that o-Cb was preferentially bound as a guest inside the cages. The stabilization of the carborane guests was attributed to various nonclassical C-HmiddotmiddotmiddotX-type interactions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yan-Na Ma, Huazhan Ren, Yanxuan Wu, Na Li, Feijing Chen, Xuenian Chen
Summary: A chemically robust and efficient synthesis route for B(9)-OH-o-carboranes has been presented in this study, where o-carboranes are oxidized using commercially available 68% HNO3 with the assistance of HOTf and HFIP. The reaction exhibits high efficiency with a wide scope of carboranes, achieving a selectivity of B(9)/B(8) up to 98:2. The success of this transformation relies on the electrophilicity and oxidizability of HNO3, which is promoted through hydrogen bonds formed by HOTf and HFIP. Mechanistic studies reveal that the oxidation of o-carborane involves an initial electrophilic attack of HNO3 to the hydrogen atom at the most electronegative B(9) position. This approach provides a selective way to incorporate carborane moieties into small molecules for boron neutron capture therapy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Kyrill Yu. Suponitsky, Sergey A. A. Anufriev, Igor B. B. Sivaev
Summary: The crystal structures of two isomeric triiodo derivatives of ortho-carborane were determined, showing different bonding patterns of iodine atoms with the carborane cage. The existence of dihalogen bonds and halogen bonds were observed in the structures. Comparison with the brominated derivative revealed similarities and differences in the bonding interactions.
Review
Chemistry, Inorganic & Nuclear
Marina Yu. Stogniy, Sergey A. Anufriev, Igor B. Sivaev
Summary: This review summarizes data on the main types of charge-compensated nido-carborane derivatives, which have increased stability compared to organic analogs. The stability is attributed to the stabilizing electron-donor action of the boron cage. The charge-compensated derivatives are discussed based on the type of heteroatom bonded to a boron atom.
Article
Chemistry, Inorganic & Nuclear
Igor B. Sivaev, Sergey A. Anufriev, Akim V. Shmalko
Summary: Based on the data of 1H NMR spectra, the effect of various substituents at boron atoms in different positions of the ortho-carborane cage on its CH-acidity and the electron-withdrawing effect upon substitution at the carbon atom is discussed. It is found that the introduction of chlorine atoms slightly reduces the CH-acidity, whereas the introduction of bromine and iodine atoms significantly increases the CH-acidity compared to the parent orthocarborane. The introduction of halogen atoms to the boron atoms bound to both carbon atoms leads to a significant increase in the CH-acidity, regardless of halogen electronegativity. However, in the case of polychlorinated derivatives of ortho-carborane, the total effect of the substituent covers the decrease in CH-acidity when the first halogen atoms are introduced into specific positions. The introduction of alkyl substituents reduces the CH-acidity, while the introduction of aryl substituents has the opposite effect.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Dmitriy K. Semyonov, Georgii K. Slushko, Marina Yu. Stogniy, Sergey A. Anufriev, Ivan A. Godovikov, Kyrill Yu. Suponitsky, Vladimir I. Bregadze, Igor B. Sivaev
Summary: The reactions of nickel(II) phosphine complexes [(dppe)NiCl2], [(MePh2P)2NiCl2] and [(Ph3P)2NiCl2] with C-substituted nido-carboranes [7-R-nido-7,8-C2B9H11]- were investigated. Different reactions were observed depending on the specific combination of reactants. Overall, the findings highlight the impact of steric interactions on the formation of nickelacarboranes.
Article
Chemistry, Multidisciplinary
K. E. Erdelyi, A. A. Antonets, O. B. Zhidkova, A. A. Druzina, A. A. Nazarov, S. V. Timofeev, I. B. Sivaev, V. I. Bregadze
Summary: Boron-containing conjugates of cholesterol were synthesized via copper(I)-catalyzed 1,3-dipolar [3+2] cycloaddition reactions. The antiproliferative activity of the conjugates was evaluated against various human cell lines, showing low toxicity and potential for cancer treatment.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Inorganic & Nuclear
Dmitriy K. Semyonov, Marina Yu. Stogniy, Kyrill Yu. Suponitsky, Igor B. Sivaev
Summary: New carboranyl thioethers were synthesized using the alkylation of the trimethylammonium salt of 1-mercapto-ortho-carborane with 1-bromo-2-methoxyethane and 1-bromo-3-methoxypropane. The deboronation of these thioethers with cesium fluoride yielded the corresponding nido-carboranes. The reactions of the nido-carboranes with various nickel(II) phosphine complexes resulted in the synthesis of nickelacarboranes.
Review
Chemistry, Multidisciplinary
Igor B. B. Sivaev
Summary: This review aims to compile the literature data on the synthesis and properties of icosahedral carborane derivatives, specifically focusing on the attachment of exo-polyhedral three- and four-coordinated boron substituents directly to the carborane cage through boron-carbon or boron-boron bonds. Various classes of compounds including carboranyl aryl boranes, boronic acids and their derivatives, boroles, diazaboroles, etc., are discussed. The review particularly highlights carborane-fused heterocycles containing boron atoms.
CHEMISTRY-SWITZERLAND
(2023)
Article
Chemistry, Inorganic & Nuclear
Varvara V. Avdeeva, Alexey S. Kubasov, Alexey V. Golubev, Sergey A. Anufriev, Igor B. Sivaev, Svetlana E. Nikiforova, Lyudmila V. Goeva, Elena A. Malinina, Nikolay T. Kuznetsov
Summary: Reactions of [B11H11]2- with copper(I) and silver(I) complexes [(Ph3P)3MX] (M = Cu, X = Cl; M = Ag, X = NO3) led to the formation of metallaboranes (Bu4N)3[commo-M(B11H11)2] instead of M-H-B complexes. The crystal structure of (Bu4N)3[Ag(B11H11)2] was determined using single-crystal X-ray diffraction. Hirschfeld surface analysis and DFT calculations were conducted for both metallaboranes [M (B11H11)2]3- (M = Cu, Ag).
INORGANICA CHIMICA ACTA
(2023)
Article
Biochemistry & Molecular Biology
Dmitriy K. Semyonov, Marina Yu. Stogniy, Sergey A. Anufriev, Sergey V. Timofeev, Kyrill Yu. Suponitsky, Igor B. Sivaev
Summary: A series of C- and B-substituted nido-carborane derivatives with a pendant pyridyl group were synthesized and used as ligands for the complexation reactions with nickel(II) and palladium(II) chlorides, forming six new metallacomplexes. The structures of these complexes were determined using single crystal X-ray diffraction.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Medicine, Research & Experimental
Satoshi Okada, Kai Nishimura, Qarri Ainaya, Kouichi Shiraishi, Sergey A. Anufriev, Igor B. Sivaev, Yoshinori Sakurai, Minoru Suzuki, Masayuki Yokoyama, Hiroyuki Nakamura
Summary: In this study, a gadolinium-boron-conjugated albumin (Gd-MID-BSA) was developed for MRI-guided neutron capture therapy. The accumulation of Gd-MID-BSA in tumors was confirmed by MRI and biodistribution analysis. The concentration ratios of boron and gadolinium in tumors satisfied the requirements for boron neutron capture therapy (BNCT) and gadolinium neutron capture therapy (GdNCT). The conjugation of gadolinium and boron in the albumin molecule enhanced the therapeutic effect of BNCT and showed potential as a promising treatment for malignant tumors.
MOLECULAR PHARMACEUTICS
(2023)
Article
Biochemistry & Molecular Biology
Anna A. Druzina, Nadezhda V. Dudarova, Ivan V. Ananyev, Anastasia A. Antonets, Dmitry N. Kaluzhny, Alexey A. Nazarov, Igor B. Sivaev, Vladimir I. Bregadze
Summary: The synthesis of the first conjugates of acridine with cobalt bis(dicarbollide) was reported. A novel 9-azido derivative of acridine was prepared and its solid-state molecular structure was determined. The obtained conjugates showed weak binding with DNA, but demonstrated potential for the development of new agents for boron neutron capture therapy (BNCT).
Article
Chemistry, Multidisciplinary
A. A. Druzina, N. V. Dudarova, I. B. Sivaev, V. I. Bregadze
Summary: A new azidoethylaminoacridine compound was synthesized and boron-containing acridine conjugates were obtained through a specific reaction. These compounds have potential applications as DNA intercalators for boron neutron capture therapy.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Inorganic & Nuclear
A. M. Zimina, T. V. Kolpakova, S. A. Anufriev, E. I. Zueva, N. V. Somov, I. B. Sivaev, I. D. Grishin
Summary: The reaction of 9-iodo-ortho-carborane with n-butylmagnesium bromide produces 9-n-butyl-ortho-carborane. Further reaction of this compound with alkali in boiling ethanol yields a new nido-carborane [5-Bu-7,8-C2B9H11](-) (I) with a n-butyl substituent. Subsequent reaction of compound I with RuCl2(PPh3)(Ph2P(CH2)(4)PPh2) leads to the formation of a ruthenium(IV) closo complex 3,3-(Ph2P(CH2)(4)PPh2)-3-H-3-Cl-9-Bu-closo-3,1,2-RuC2B9H10 (II) characterized by 2D NMR spectroscopy. Heating compound II with carbon tetrachloride results in the formation of the 17-electron complex 3,3-(Ph2P(CH2)(4)PPh2)-3-Cl-9-Bu-closo-3,1,2-RuC2B9H10, and the structure of this complex is determined using X-ray diffraction.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2023)
Review
Chemistry, Physical
Varvara V. Avdeeva, Svetlana E. Nikiforova, Elena A. Malinina, Igor B. Sivaev, Nikolay T. Kuznetsov
Summary: In this article, composites and materials prepared from boron hydride cluster compounds are presented. The utilization of these materials as boron protective coatings, as well as their applications in synthesizing boron carbide, boron nitride, metal borides, metal-containing composites, and neutron shielding materials, are discussed.