Article
Polymer Science
Noelia Esteban, Miguel Claros, Cristina Alvarez, Angel E. Lozano, Camino Bartolome, Jesus M. Martinez-Ilarduya, Jesus A. Miguel
Summary: A new set of microporous organic polymers (POPs) with high microporosity and moderate thermal stability has been synthesized via Friedel-Crafts knitting. These polymers, containing diphosphine derivatives, act as efficient catalysts for Suzuki-Miyaura coupling reactions, exhibiting excellent recyclability.
Article
Chemistry, Multidisciplinary
Matteo Albino, Thomas J. Burden, Carmen C. Piras, Adrian C. Whitwood, Ian J. S. Fairlamb, David K. Smith
Summary: The increase in demand and low abundance of palladium pose a significant threat to its future availability, making research into sustainable palladium-based technologies crucial. This study reports the development of Pd scavenging hybrid gel beads composed of agarose and a low-molecular-weight gelator based on DBS-CONHNH2. These mechanically robust gel beads exhibit potential as practical catalysts for Suzuki-Miyaura cross-coupling reactions, demonstrating good reusability, green metrics, and improved reaction times compared to previous examples. The leaching of palladium is almost completely eliminated and a detailed investigation explains how the nanoparticles are formed in situ. These ligand-free gel beads can be considered as robust nonligated heterogeneous PdNP catalysts with potential for the development of easily used chemical reaction systems.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Applied
Mingyang Gao, Jiamin Wang, Weixiang Shang, Yuchao Chai, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li
Summary: Suzuki-Miyaura cross-coupling reaction is a powerful method to construct carbon-carbon bonds and is widely used in the synthesis of functional organic compounds. In this study, zeolite-encased Pd particles (Pd@MFI) were successfully prepared and investigated as promising heterogeneous catalysts for the Suzuki-Miyaura cross-coupling reaction. The Pd@MFI catalysts showed high activity, with dispersed Pd particles efficiently stabilized within the MFI zeolite matrix. The presence of basic sites adjacent to Pd sites was crucial for achieving high catalytic activity.
Article
Chemistry, Multidisciplinary
Julius Hoepfner, Marius Brehm, Pavel A. Levkin
Summary: The rising costs of pharmaceutical research are currently limiting the productivity of drug discovery and development, but can potentially be reduced through miniaturization of compound synthesis and screening. In this study, the influential palladium-catalyzed Suzuki-Miyaura reaction is successfully implemented at the nanoliter scale on droplet microarrays for the synthesis of an 800-compound library of biphenyls. The synthesis of these compounds requires minimal reagents and solvent volume, and the obtained compounds can be purified and cleaved from excess reactants and catalyst. This novel approach expands the capabilities of droplet microarrays for miniaturized high-throughput chemical synthesis and opens up possibilities for future synthesis and screening of chemical compounds in a single platform.
Article
Chemistry, Physical
Matthew J. Andrews, Sebastian Brunen, Ruaraidh D. McIntosh, Stephen M. Mansell
Summary: This paper describes the synthesis and catalytic testing of a palladium complex with a 5-membered chelating [N,O] ligand, derived from the condensation of 2,6-diisopropylphenyl aniline and maple lactone. The catalyst was active towards the Suzuki-Miyaura cross-coupling reaction, and its activity was optimised through the selection of base, solvent, catalytic loading and temperature. The catalyst exhibited good activity towards aryl bromides with electron-withdrawing groups, as well as a range of boronic acids and pinacol esters. It was also a capable catalyst for the cross-coupling of aryl chlorides and phenylboronic acid.
Article
Chemistry, Applied
Kanticha Khomthawee, Nattaporn Nilada, Antika Homchuen, Pranorm Saejueng
Summary: The CS-EDTA-Pd catalyst was prepared by dissolving chitosan and EDTA in acetic acid, forming beads, adsorbing palladium(II), and reducing it to palladium(0) with ethanol reflux. The catalyst was characterized by various techniques. It was then tested in the Suzuki-Miyaura cross-coupling reaction and showed good catalytic activity. The catalyst is inexpensive, easy to prepare, and can be reused multiple times with only a slight loss in product yields.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Arputham Shophia Lawrence, Nuria Martin, Balasubramanian Sivakumar, Francisco G. Cirujano, Amarajothi Dhakshinamoorthy
Summary: Among cross coupling reactions, C-C cross coupling reaction has attracted much attention and progress in the past four decades. Pd, one of the transition metals, has shown the highest activity due to its unique features and reactivity. However, due to the high cost and self-deactivation of Pd-based homogeneous catalysts, researchers have turned their focus towards the development of Pd-based heterogeneous catalysts. Metal organic frameworks (MOFs) have been frequently used as host matrix for the deposition of Pd(II) salts and Pd nanoparticles. This review provides a design and development of Pd-based MOFs as heterogeneous catalysts for C-C cross coupling reactions.
Article
Chemistry, Physical
Jonathan De Tovar, Franck Rataboul, Laurent Djakovitch
Summary: This review discusses the potential application and understanding of Pd(II) complexes anchored on different supports as catalytic systems for the Suzuki-Miyaura reaction, highlighting their high reactivity, easy separation, purification, and recyclability. It focuses on the general developments in this research area over the last three decades, including the most recent achievements and understanding of these heterogenized systems.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Multidisciplinary
Angus Olding, Curtis C. Ho, Allan J. Canty, Nigel T. Lucas, James Horne, Alex C. Bissember
Summary: This study reports the synthesis of a family of unprecedented arylpalladium(II) boronates that are kinetically stable at ambient temperature, and their chemical competence in a Suzuki-Miyaura reaction was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sheng-Qi Qiu, Yu Chen, Xiang-Jun Peng, Shi-Jiang He, Jun Kee Cheng, Yong-Bin Wang, Shao-Hua Xiang, Jun Song, Peiyuan Yu, Junmin Zhang, Bin Tan
Summary: In this study, we achieved the arene-alkene Suzuki-Miyaura coupling reaction between hindered aryl halides and vinyl boronates by designing appropriate ligands and reaction parameters. The axially chiral acyclic aryl-alkenes obtained exhibited remarkable efficiency, enantioselectivity, and E/Z selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhenzhong Zhang, Aya Ohno, Hikaru Takaya, Yoichi M. A. Yamada
Summary: Researchers developed a catalyst for Suzuki-Miyaura coupling under flow conditions using a molecular convolution method. The catalyst showed high performance and durability, allowing for the continuous synthesis of two pharmaceuticals in water as the sole solvent.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Nanoscience & Nanotechnology
Hao Zhang, Xingcong Zhang, Shaolin Shi, Qian He, Xiaohui He, Tao Gan, Hongbing Ji
Summary: This study presents a facile method for the synthesis of high-productivity noble metal single-atom catalysts through direct ball milling. The as-prepared catalysts show excellent catalytic performance for the Suzuki-Miyaura cross-coupling reaction. Moreover, kilogram-scale synthesis of these catalysts is achieved in one batch, indicating great potential for industrial applications.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Review
Chemistry, Physical
Gianluigi Albano, Antonella Petri, Laura Antonella Aronica
Summary: In recent years, there has been extensive research on immobilizing palladium nanoparticles on solid supports for the preparation of active and stable catalytic systems. Compared to inorganic materials, naturally occurring organic solids are more cost-effective and readily available. This review focuses on the application of metal catalysts supported by natural biomaterials in C-C bond formation reactions, specifically Mizoroki-Heck, Suzuki-Miyaura, and Sonogashira reactions. Different types of organic matrices, such as cellulose, starch, pectin, agarose, chitosan, as well as proteins and enzymes, are discussed, highlighting the heterogeneous nature and recyclability of each catalyst.
Article
Polymer Science
Afaf Y. Khormi, Mohamed Abboud, Mohamed S. Hamdy, Murad Eissa, Mohamed R. Shaaban
Summary: The paper describes the synthesis of a novel nano-sized phosphine-free benzothiazole-based palladium(II) complexes and their efficiency as catalysts for Suzuki Miyaura cross coupling reaction using water as a solvent under microwaves irradiations. The catalytic activity of the novel nanocatalysts for SMC of aryl halides with arylboronic acids using water as a solvent and under microwaves irradiation conditions was investigated.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2023)
Article
Chemistry, Physical
Antonio J. LaPorte, Yao Shi, Jason E. Hein, Martin D. Burke
Summary: Stereospecific Csp(3) Suzuki-Miyaura cross-coupling simplifies the synthesis of stereochemically complex small molecules, but current methods are not compatible with complex building blocks commonly found in natural products and other complex targets. This study presents a method for embedding the alpha-methyl-beta-hydroxyl motif within stereochemically defined secondary alkyl boronic ester building blocks, allowing for stereospecific cross-coupling. The use of beta-aryloxysilyl groups addresses the decrease in reactivity and side reactions associated with beta-oxygen-containing Csp(3) boronic esters. Mechanistic studies reveal the activation of a dihydroxysiloxaborolate as a transmetalation partner in a stereospecific process that retains configuration.
Article
Chemistry, Inorganic & Nuclear
Mikhail A. A. Kinzhalov, Daniil M. M. Ivanov, Anastasia V. V. Shishkina, Anna A. A. Melekhova, Vitalii V. V. Suslonov, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. A. Bokach
Summary: Crystallization of [CuI(CNXyl)(3)] (1) with I-2 resulted in the formation of a series of (XylNC)Cu-I crystal polyiodides, along with the accumulation of iodine. The compounds [Cu(I-3)(CNXyl)(3)] (2(I) and 2(II)), [Cu(I-3)(CNXyl)(3)]center dot 1/2I(2) (2 center dot 1/2I(2)), and [Cu(CNXyl)(3)](I-5) (3) were studied by X-ray diffractometry. The presence of an I-2?I-3(-) halogen bonded linkage in the structure of 2 center dot 1/2I(2) provides insight into the mechanism for the generation of I-5(-) and I-8(2-) ligands from I-2 and metal-coordinated I-3(-).
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Anton V. V. Rozhkov, Eugene A. A. Katlenok, Margarita V. V. Zhmykhova, Maxim L. L. Kuznetsov, Victor N. N. Khrustalev, Kirill I. I. Tugashov, Nadezhda A. A. Bokach, Vadim Yu. Kukushkin
Summary: This study investigates the properties of platinum(II) complexes and anticrown cocrystals with stacked heteroplanar architectures. The results demonstrate that the spodium bonds between Hg···Pt and Hg···C play a crucial role in controlling the stacking orientation. Heteroplanar stacking enhances the phosphorescence lifetimes and solid-state quantum yield.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Andrey S. S. Smirnov, Alexander S. S. Mikherdov, Anton V. V. Rozhkov, Rosa M. M. Gomila, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. A. Bokach
Summary: Co-crystallization of 1,4-diisocyanobenzene (1) and 1,4-diisocyanotetramethylbenzene (2) with halogen bond donors such as 1,4-diiodotetrafluorobenzene (1,4-FIB) and 4,4'-diiodoperfluorobiphenyl (4,4'-FIBP) resulted in the formation of co-crystals 1 . 1,4-FIB, 1 . 4,4'-FIBP, and 2 . 1,4-FIB. The solid-state structures showed 1D-supramolecular arrangements based on poorly explored I...C halogen bonding, and the use of tetraiodoethylene (TIE) resulted in a 3D-framework supramolecular architecture in the structure of 1 . TIE. DFT calculations indicated moderately strong I...C non-covalent interactions, and NBO analysis revealed relevant LP(C)->sigma* charge transfer effects in all co-crystals.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yulia N. Toikka, Galina L. Starova, Vitalii V. Suslonov, Rosa M. Gomila, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. Bokach
Summary: Cocrystallization of CuI with NCNMe2 in the presence of 1,4-diiodotetrafluorobenzene (1,4-FIB) and 1,4-dibromotetrafluorobenzene (1,4-FBrB) in MeCN resulted in the formation of three cocrystals. The solid-state structures of these cocrystals were studied using X-ray diffraction. Perfluorinated haloarenes act as combined sigma- and pi-hole donors and form intermolecular contacts with the copper clusters through halogen bonding and pi-hole interactions with the iodine ligands. Theoretical calculations suggest that the formation of (cubane)•(perfluorinated haloarene) pi-hole dimer is slightly more energetically favorable than (cubane)•(perfluorinated haloarene) HaB-based sigma-hole dimer. These interactions involve additional hydrogen bonding and pi-hole(N-CN)•••X (X = Br, I) contacts, leading to moderately strong noncovalent binding between the copper clusters and the aromatic HaB donors.
CRYSTAL GROWTH & DESIGN
(2023)
Review
Biochemistry & Molecular Biology
Sergey V. V. Baykov, Anton A. A. Shetnev, Artem V. V. Semenov, Svetlana O. O. Baykova, Vadim P. P. Boyarskiy
Summary: This review discusses synthetic methods for obtaining 1,2,4-oxadiazole and their application in pharmaceutical preparation. The methods are divided into three groups, including two-stage protocols, one-pot synthesis, and oxidative cyclization. These methods have significant potential in drug design, allowing for the preparation of thermosensitive 1,2,4-oxadiazole and expanding the use of oxadiazole core as a linker in bioactive compound design.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Svetlana O. Baykova, Kirill K. Geyl, Sergey V. Baykov, Vadim P. Boyarskiy
Summary: A new synthetic route for quinazolin-2,4(1H,3H)-diones and thieno[2,3-d]pyrimidine-2,4(1H,3H)-diones substituted by pyridyl/quinolinyl moiety in position 3 has been developed. The method involves the annulation of substituted anthranilic esters or 2-aminothiophene-3-carboxylates with 1,1-dimethyl-3-(pyridin-2-yl) ureas, forming N-aryl-N'-pyridyl ureas and subsequent cyclocondensation into the desired heterocycles. The reaction exhibits moderate to good yields (up to 89%) and can be easily scaled to gram quantities.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Applied
Nikolay V. V. Shcherbakov, Polina F. F. Kotikova, Elena I. I. Chikunova, Dmitry V. V. Dar'in, Vadim Yu. Kukushkin, Alexey Yu. Dubovtsev
Summary: The gold-catalyzed interplay between ynamides and aminocarbonyls provides a pathway to 2-aminoquinolines. This modular annulation reaction occurs under mild conditions and is compatible with various functionalities. Unlike other gold-catalyzed methods, this approach allows for the use of diverse aminocarbonyl substrates and allows for the variation of substituents in the 4th position of the quinoline. The obtained heterocyclic products demonstrate synthetic potential through post-modifications of the quinoline backbone and peripheral substituents.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Amirbek D. Radzhabov, Natalia S. Soldatova, Daniil M. Ivanov, Mekhman S. Yusubov, Vadim Yu. Kukushkin, Pavel S. Postnikov
Summary: We have developed an efficient strategy for the synthesis of diarylselenides using iodonium salts as reactants. This method allows the conversion of trimethoxyphenyl-substituted iodonium salts to diarylselenides in a two-step one-pot reaction sequence. The reaction involves the participation of both iodonium aryl groups for diarylation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: By using X-ray crystallography, the cocrystals 1 center dot C6F6, 2 center dot C6F6, and 1 center dot(OFA)(2) were obtained by crystallizing the half-lantern Pt-2(II) complexes with electron-deficient arenes. The structural data revealed the occurrence of π-π stacking between the arenes and metal square-planes. Density functional theory calculations and orbital interaction analysis confirmed the contribution of noncovalent bonding and charge-transfer interaction in the overall stacking forces.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: In this study, it was observed by X-ray crystallography that the Pt-2(II) complexes form crystals with electron-deficient arenes, and it was verified that there is a π-π stacking interaction between the arenes and the metal square-planes. Density functional theory calculations confirmed the contribution of the noncovalent bond between the arenes and Pt(II) in the overall stacking forces. Orbital interaction analysis demonstrated the significance of the charge-transfer interaction between d(z)(2)(Pt) and pi*(C), attributing the C.Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis showed a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. A. Katlenok, Maxim L. L. Kuznetsov, Nikolay A. A. Semenov, Nadezhda A. A. Bokach, Vadim Yu. Kukushkin
Summary: The solid-state structures of co-crystals of chalcogenadiazoles with planar half-lantern Pt2 and mononuclear Pt complexes exhibit short Ch.Pt contacts. A comprehensive DFT study revealed that the platinum(II) center does not interact with the deep s-holes of chalcogenadiazoles but is involved in other types of interactions, including with a p-hole at the chalcogenadiazoles site. The unusual linkage between a platinum(II) atom and chalcogenadiazoles is driven by the combined action of Pt.p-hole on Ch bonding and other C.C/C.S p-hole interactions.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
S. A. Katkova, E. V. Sokolova, M. A. Kinzhalov
Summary: A series of platinum(II) cyclometallated complexes with two isocyanide ligands were synthesized and characterized. Their structure was determined by various spectroscopic techniques and their photophysical properties and mechanochromic luminescence behavior were studied in the solid state.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Svetlana A. Katkova, Daria O. Kozina, Kristina S. Kisel, Maria A. Sandzhieva, Dmitriy A. Tarvanen, Sergey V. Makarov, Vitaly V. Porsev, Sergey P. Tunik, Mikhail A. Kinzhalov
Summary: A series of cyclometalated platinum(ii) complexes with acyclic diaminocarbene (ADC) ancillary ligands were designed and synthesized. Their photophysical properties were investigated both experimentally and theoretically. The complexes showed green phosphorescence with high quantum efficiency of up to 45% in 2 wt% doped PMMA film at room temperature. These complexes were further utilized as light-emitting dopants for OLED fabrication. The resulting devices demonstrated green emission with a maximum current efficiency of 2.9 cd A(-1) and a luminance of 2700 cd m(-2), highlighting the potential of these cyclometalated platinum(ii) complexes as efficient green emitters for OLED devices.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Maria V. Kashina, Andrei A. Karcheuski, Mikhail A. Kinzhalov, Konstantin V. Luzyanin, Svetlana A. Katkova
Summary: A series of platinum complexes with phosphine and isocyanide ligands were synthesized and evaluated as catalysts for photocatalytic hydrosilylation of alkynes. The phosphine-isocyanide complexes showed high yields under violet light irradiation, while the parent phosphine complexes were more efficient under blue light irradiation.
