Review
Chemistry, Multidisciplinary
Takashi Koike, Munetaka Akita
Summary: The electron is unique and has the ability to participate in various systems, with novel electron injection methods revolutionizing chemical bond formation techniques in organic synthesis. In particular, visible-light organic photoredox catalysis has rapidly spread among synthetic chemists due to its sustainability and versatility.
TRENDS IN CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Rajeshwar Reddy Aleti, Alexey A. Festa, Leonid G. Voskressensky, Erik V. van der Eycken
Summary: Phenanthridinones, important heterocyclic frameworks, have attracted great interest in organic synthesis and medicinal chemistry for developing new synthetic methodologies and pharmaceutical compounds.
Article
Chemistry, Multidisciplinary
Friederike Ratsch, Joss Pepe Strache, Waldemar Schlundt, Joerg-Martin Neudoerfl, Andreas Adler, Sarwar Aziz, Bernd Goldfuss, Hans-Guenther Schmalz
Summary: The Ir-catalyzed conversion of prochiral tert-cyclobutanols to beta-methyl-substituted ketones in toluene under mild conditions is effective for the enantioselective desymmetrization of substrates, yielding products with quaternary chirality centers with high ee values. The mechanistic differences compared to related Rh-I-catalyzed transformations were revealed through deuterium experiments and kinetic isotope effect measurements. The computational model proposed the initial formation of an Ir-III hydride intermediate and its subsequent beta-C elimination, allowing prediction of the stereochemical outcome.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Applied
Ahmad Saifuddin Mohamad Arshad, Mohd Nizam Mordi
Summary: Carbolines are a prominent class of tricyclic alkaloids found in natural products, and there are four different regioisomers known. Synthetic methods have been established for the construction of carboline frameworks, both requiring customized approaches for each regioisomer and unified approaches capable of generating multiple regioisomers. This review summarizes the construction of isomeric carbolines based on unified synthetic approaches.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Yuna Nishiguchi, Katsuhiko Moriyama
Summary: A new synthetic method was developed with the use of aniline-type hypervalent iodine(III) for direct cyclizations, resulting in high yields of the corresponding products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Applied
Xiaofan Cui, Remi Chauvin, Chao Pi, Yangjie Wu, Xiuling Cui
Summary: This review presents recent progress in the use of vinylene carbonate as a reactant in transition metal-catalyzed C-H bond activation/cyclization reactions. By analyzing and comparing different reaction models, it highlights the advantages of using vinylene carbonate as a surrogate for ethynol and other reactants, and discusses related mechanisms and synthetic applications.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Youliang Zou, Binfeng Zhang, Li Wang, Hua Zhang
Summary: A benzoic acid-promoted C2-H borylation of indoles with pinacolborane is developed, providing a prompt route toward the synthesis of diverse C2-functionalized indoles. Preliminary mechanistic studies suggest that BH3-related borane species formed via the decomposition of pinacolborane may be the probable catalyst.
Article
Chemistry, Multidisciplinary
Chao Zheng, Shu-Li You, Chen-Xu Liu, Pei-Pei Xie, Fangnuo Zhao, Quannan Wang, Zuolijun Feng, Haoyang Wang
Summary: Through comprehensive experimental and computational studies, the mechanism of Rh(I)-catalyzed C-H arylation has been elucidated, including the identification of each elementary step in the catalytic cycle and the structural characterization of key intermediates and transition states. This research provides a foundation for the rational design and development of challenging intramolecular reactions and successfully realizes the facile synthesis of planar chiral [m]ferrocenophanes, a class of rarely explored target molecules with strained structures and intriguing molecular topology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Organic
Jiaming Liu, Ming Chen
Summary: This review focuses on the preparation methods and reactions of 1,3-bifunctional nucleophilic allylation reagents, as well as their synthetic applications in complex molecule synthesis.
SYNTHESIS-STUTTGART
(2021)
Review
Chemistry, Physical
Sebastian Barata-Vallejo, Damian E. Yerien, Al Postigo
Summary: Due to the need for more environmentally friendly processes in synthetic organic chemistry, the use of photocatalysts found in nature and mimicking natural processes to achieve organic transformations is highly appealing. This article discusses the photocatalysis of oxidation, reduction, carbon-oxygen, carbon-carbon and carbon-sulfur bond formation reactions, as well as E-Z geometrical isomerization reactions, using biological natural pigments, vitamins, cofactors, and compounds with antiviral activity.
Article
Chemistry, Applied
Xinjiao Hou, Run Wang, Jianhui Zhou, Yuan Li, Jiyuan Li, Hong Liu, Dechuan Wang, Yu Zhou
Summary: A substrate and catalyst-controlled synthetic strategy was used to construct two different types of fused polycyclic heterocycles. This method can rapidly generate the two different polycyclic scaffolds through a simple C-H activation and cyclization cascade pathway. Sulfoxonium ylides played a crucial role in both transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Neha Jha, Nandkishor Prakash Khot, Manmohan Kapur
Summary: The past decade has seen significant advancements in transition-metal-catalyzed C-H bond activation and carbene migratory insertion reactions, facilitating the construction of diverse arene/heteroarene scaffolds. Various transition-metal catalysts are utilized for easy access to substituted heterocycles, with key mechanistic pathways involving C-H activation, diazo insertion, and subsequent coupling reactions.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Luke Britton, Jamie H. Docherty, Jan Sklyaruk, Jessica Cooney, Gary S. Nichol, Andrew P. Dominey, Stephen P. Thomas
Summary: C-H functionalisation reactions are important for sustainable molecular construction and diversification, but are mainly catalyzed by precious metals. In this study, iron-catalyzed C(sp(2))-H bond hydrogen/deuterium exchange reactions were investigated in heterocycles and alkenes, providing evidence for reversible protonation of the active iron hydride catalyst. This research has implications for future discovery and development.
Article
Chemistry, Multidisciplinary
Jiang-Fei Li, Deng Pan, Hao-Rui Wang, Tao Zhang, Yi Li, Genping Huang, Mengchun Ye
Summary: A chiral phosphine oxide-ligated Ni-Al bimetallic catalyst was successfully utilized for an enantioselective C2-H alkylation of pyridines, showing compatibility with a wide range of pyridine substrates and providing high yields and enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Tomas Chlupaty, Zdenka Ruzickova, Hana Kampova, Jan Merna, Ales Ruzicka
Summary: The synthesis and structure of lithium, magnesium, and zinc complexes chelated by hybrid amine-amido ligands are reported. These complexes can be prepared through various reactions and have diverse forms.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dominik Vitek, Ales Ruzicka, Lise Vermeersch, Libor Dostal, Jan Turek, Roman Jambor
Summary: Reactivity studies and theoretical calculations were conducted to investigate the effect and tuning of Germanium (Ge) donation to Boron (B) in the complex L-(CI)Ge⋅BH3. N-coordinated compounds and their bonding properties were synthesized and evaluated experimentally. The results revealed the possibility of tuning the Ge→B coordination and the strength of Ge→B donation. The findings were further supported by energy decomposition analysis and proton affinity assessment.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Miroslav Novak, Jan Turek, Yaraslava Milasheuskaya, Miriam Sykova, Libor Dostal, Jesse Stalmans, Zdenka Ruzickova, Klaus Jurkschat, Roman Jambor
Summary: A series of novel non-symmetric neutral N, N', O-chelating ligands derived from alpha-iminopyridine were synthesized and their reactivity with SnCl2 and Sn(OTf)2 was investigated. The steric and electronic properties of the ligands and the resulting products were studied using DFT calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Dominik Vitek, Ales Ruzicka, Libor Dostal, Roman Jambor
Summary: The effect of chelating ligands and Ge->B interaction on the strength of the Ge OtBu bond was studied, which resulted in the isolation of Ge(II) carbamate. Alcoholysis exchange reactions between substituted phenols and compounds 1 and 2 were studied to synthesize functionalized Ge(II) alkoxides. Phosphane-decorated Ge(II) alkoxides were tested as ligands in reactions with (COD)W(CO)(4) and BH3, leading to the isolation of new complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Tatyana S. Koptseva, Alexandra A. Skatova, Sergey Yu. Ketkov, Elena A. Rychagova, Roman V. Rumyantcev, Igor L. Fedushkin
Summary: The reduction of diolate [{(dpp-bian)Al(mu- O2CH2)}2] (1), bearing a redox-active acenaphthene-1,2-diimine ligand, by boranes has been investigated. Different products are obtained depending on the specific borane used. The molecular structures of the products have been determined and the reaction energies analyzed using density functional theory calculations.
Article
Chemistry, Applied
Anna Hruzikova, Lucie Muzikova Cechova, Sille Stepanova, Lucie Tuckova, Marketa Tichotova, Ales Ruzicka, Vaclav Kasicka, Eliska Prochazkova
Summary: Azopyrimidines are a new class of photoswitches that can switch between trans and cis isomers. Their low solubility in water limits their biological applications, but this can be overcome by inclusion into supramolecular structures. Our research focuses on the structure, isomerization, and host-guest chemistry of azopyrimidines with cyclodextrins. We found that beta-cyclodextrin exhibits high selectivity for the accommodation of these compounds.
Article
Chemistry, Inorganic & Nuclear
Marina A. Katkova, Galina S. Zabrodina, Roman. Rumyantcev, Grigory Yu. Zhigulin, Maria S. Muravyeva, Andrey S. Shavyrin, Dmitriy G. Sheven, Sergey Yu. Ketkov
Summary: The increased interest in water-soluble aminohydroximate Ln(III)-Cu(II) metallacrowns (MC) is driven by their fascinating structural chemistry, diverse properties, and simple synthesis. We investigated the water-soluble praseodymium (III) alaninehydroximate complex Pr(H2O)4[15-MCCu(II)Alaha-5]center dot 3Cl (1) as an effective chiral lanthanide shift reagent for NMR analysis of biologically relevant (R/S)-mandelate (MA) anions in water. The enantiomers R-MA and S-MA can be easily distinguished in the presence of small amounts of MC 1 by the 1H NMR signals of multiple protons with an enantiomeric shift difference (Delta Delta delta) ranging from 0.06 ppm to 0.31 ppm. Additionally, the possibility of MA coordination to the metallacrown was investigated using ESI-MS technique and Density Functional Theory modeling.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Petr Svec, Iva Vranova, Zdenka Ruzickova, Maksim A. Samsonov, Libor Dostal, Ales Ruzicka
Summary: A series of organoantimony(III/V) and organobismuth(V) fluorides with a C,N-chelating ligand (L) were synthesized using LCNR2SnF and/or XeF2 as fluorinating agents. The compounds were characterized by elemental analysis, multinuclear solution NMR spectroscopy, and single crystal XRD analysis. The experimental results were supported by theoretical calculations. The preparation and structural characterization of LSbI2 were also reported. (c) 2023 Elsevier B.V. All rights reserved.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jan Zechovsky, Erik Kertesz, Milan Erben, Roman Jambor, Ales Ruzicka, Zoltan Benko, Libor Dostal
Summary: The reactivity of pnictinidenes towards substituted ortho- and para-quinones was studied. Ortho-quinones oxidized the central pnictogen atom, while in the case of arsenic compounds, a new azaarsole ring was formed. Heating these arsenic heterocycles resulted in a C-H bond activation and reductive elimination. Para-quinones also oxidized the central atom and led to hydrogen migration, with feasible reductive elimination.
Article
Nanoscience & Nanotechnology
Yongan Zhu, Wei Lu, Tongtong Gu, Xin Gao, Naisen Yu, Sergey Yu. Ketkov, Zhenyi Zhang
Summary: We developed a plasmonic semiconductor photodetector based on W18O49 nanowire array (NWA) to achieve a tunable broadband photodetector. By adjusting the plasmonic absorption intensity of the W18O49 NWA through manipulating the free electron density with an external voltage, the responsivity and detectivity of the photodetector in the visible-NIR region were significantly increased. The proposed strategy of using low-cost nonmetallic plasmonic nanostructures offers a promising way to construct broadband-tunable photodetectors.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Felix Feige, Lorraine A. Malaspina, Florian Kleemiss, Julius F. Koegel, Sergey Ketkov, Emanuel Hupf, Simon Grabowsky, Jens Beckmann
Summary: The perfluorinated alkoxy silanes were synthesized and fully characterized. However, attempts to deprotonate them to form the conjugate silanide ions failed due to the exceptionally short and strong Si-H bonds. In the solid state, the Si-H units do not participate in any intermolecular interactions, and the crystal packing is dominated by exceptionally short and strong F...F interactions. The cohesive energies are solely attributed to London dispersion interactions, similar to noble gas crystal structures.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Anastasia Yu. Gitlina, Stanislav Petrovskii, Maksim Luginin, Alexey Melnikov, Elena Rychagova, Sergey Ketkov, Elena Grachova
Summary: This study investigates a new series of luminescent cyclometalated complexes as "building blocks" for constructing a supramolecular network. The complexes exhibit non-covalent interactions in the crystal state, and their emission profiles are mainly determined by the nature of the C ligand, as revealed by DFT calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jan Zechovsky, Vit Kremlacek, Milan Erben, Martin Hejda, Elena Rychagova, Roman Jambor, Ales Ruzicka, Sergey Ketkov, Libor Dostal
Summary: This paper reports the reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound towards an electron-deficient alkyne, dimethyl acetylenedicarboxylate (DMAD). The reactions show significant examples of element-ligand cooperation. The compounds react via dearomatization of a latent heteropnictole ring, producing rare examples of hetero Diels-Alder (DA) adducts. Furthermore, the study includes a theoretical survey to describe the main thermodynamic parameters and reaction pathways.
DALTON TRANSACTIONS
(2022)
