Article
Chemistry, Inorganic & Nuclear
Laia Rafols, Dana Josa, David Aguila, Leoni A. Barrios, Olivier Roubeau, Jordi Cirera, Vanessa Soto-Cerrato, Ricardo Perez-Tomas, Manuel Martinez, Arnald Grabulosa, Patrick Gamez
Summary: The newly synthesized compounds showed poor cytotoxic activities in cell cultures, but displayed improved activities in aged DMSO solutions. It was found that the compounds underwent transformation reactions in DMSO, ultimately forming cyclometalated species.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Bishnu Das, Parna Gupta
Summary: Square planar Pt(II) complexes were reported as luminescent biosensors for DNA detection, with the bright red photoluminescence induced by aggregation serving as the sensing mechanism. The study explored terpyridine-appended geminal bistriazoles for metal coordination, resulting in tetranuclear and dinuclear Pt(II) complexes with different ligand environments. This is the first report of terpyridine-appended geminal bistriazoles in the literature.
DALTON TRANSACTIONS
(2021)
Article
Biochemistry & Molecular Biology
Francesca Sacco, Matteo Tarchi, Giarita Ferraro, Antonello Merlino, Giorgio Facchetti, Isabella Rimoldi, Luigi Messori, Lara Massai
Summary: The study investigated the reactions of three novel platinum(II) complexes with model proteins through ESI MS analysis, revealing diverse reactivity patterns depending on the nature of the Pt complex and interacting proteins. The formation of protein-bound Pt fragments was identified, and crystal structures were used to determine the exact location of Pt binding sites, contributing to understanding the potential mechanisms of action of these innovative anticancer Pt complexes.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Organic
Saravanan Gowrisankar, Bastian Bernhardt, Jonathan Becker, Peter R. Schreiner
Summary: New meta-substituted tetraaryl adamantane derivatives were synthesized in one step through Friedel-Crafts adamantylation using AlCl3 and t-butyl bromide. These products exhibit improved highly directional white-light emission compared to tetraphenyl adamantane upon irradiation with a continuous wave laser diode.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Nikolai F. Romashev, Pavel A. Abramov, Ivan Bakaev, Iakov S. Fomenko, Denis G. Samsonenko, Alexander S. Novikov, Kelvin K. H. Tong, Dohyun Ahn, Pavel Dorovatovskii, Yan Zubavichus, Aleksey A. Ryadun, Olga A. Patutina, Maxim N. Sokolov, Maria Babak, Artem L. Gushchin
Summary: A series of Pt and Pd complexes with dpp-Bian and different ligands were synthesized and characterized. The Pt(dpp-Bian) complexes showed high anticancer activity at low concentrations and exhibited selectivity towards cancer cells. These complexes induced the generation of reactive oxygen species in cancer cells and were able to intercalate into DNA.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jaegyeong Lee, Iuliia Melchakova, Saira Nayab, Kyeonghun Kim, Young Ho Ko, Minyoung Yoon, Paul Avramov, Hyosun Lee
Summary: In this study, Zn(II), Pd(II), and Cd(II) complexes supported by the (E)-N-1,N-1-dimethyl-N-2-(thiophen-2-ylmethylene)ethane-1,2-diamine (LTH) ligand were synthesized and structurally characterized. The presence of two conformers and their dynamic interconversion process in solution was supported by DFT calculations and variable-temperature NMR. These complexes exhibited different geometric structures and could effectively catalyze the ring-opening polymerization of rac-lactide, with [LTHZnCl2]/(LiOPr)-Pr-I showing the highest conversion rate and producing PLA with higher heterotactic bias.
Article
Biochemistry & Molecular Biology
Ruchika Ojha, Peter C. Junk, Alan M. Bond, Glen B. Deacon
Summary: Pt-IV coordination complexes were synthesized by oxidizing the antitumor agent [Pt-II(p-BrC6F4)NCH2CH2NEt2}Cl(py)]. Experimental data showed that excess H2O2 and elevated temperature favored the oxidation of the ligand, while a smaller amount of H2O2 at room temperature favored the oxidation of the metal, resulting in the formation of platinum(IV) complexes.
Article
Chemistry, Multidisciplinary
Nandini Savoo, Chahlaa Mungur, Lydia Rhyman, Ponnadurai Ramasami, John A. A. Joule
Summary: The preferred site for electrophilic aromatic substitution reactions of thiophene 1 and thieno[2,3-b]thiophene 2 was determined using N-chlorosuccinimide electrophile in the gas phase and in acetic acid. The SEAr reaction mechanisms were investigated employing B3LYP/6-311G(d), B3LYP-D3/6-311G(d), and M06-2X/6-311G(d) methods. It was found that the alpha-carbon atom was preferred over the beta-carbon atom for electrophilic attack in both 1 and 2, both kinetically and thermodynamically.
PURE AND APPLIED CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pascal Jurt, Anne Sofie Abels, Juan Jose Gamboa-Carballo, Israel Fernandez, Gregoire Le Corre, Marcel Aebli, Matthew G. Baker, Frederik Eiler, Fabian Mueller, Michael Worle, Rene Verel, Sebastien Gauthier, Monica Trincado, Thomas L. Gianetti, Hansjorg Grutzmacher
Summary: A bimetallic Rh-I-Pt-II complex with a specially designed multidentate phosphine olefin ligand can catalytically detoxify nitrogen oxides, forming water and N-2 as benign products at room temperature. Investigation into the conversion process revealed the generation of a hyponitrite (N2O22-) complex as an intermediate, shedding light on a possible reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Kevin Morales, Sergi Rodriguez-Calado, Jordi Hernando, Julia Lorenzo, Antonio Rodriguez-Dieguez, Carlos Jaime, Pau Nolis, Merce Capdevila, Oscar Palacios, Marta Figueredo, Pau Bayon
Summary: This study presents the synthesis, characterization, photochemical properties, and cytotoxic activity of new semisquaraine-type Pt(II) complexes towards cisplatin-resistant cancer cell lines. The complexes showed promising photoactivatable properties, inducing a higher cytotoxic effect on tested cells compared to nonphotoactivated compounds. The mechanism of action of these complexes was studied, revealing a combined mode of action. The results suggest a therapeutically potential advantage of these photoactivated platinum complexes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Luyao Niu, Guolian Ren, Tianjiao Hou, Xuan Shen, Dunru Zhu
Summary: Three luminescent Pt(II) complexes were synthesized and showed potential as DNA luminescent probes and in anticancer activities. Among them, complex 3 exhibited the highest cytotoxicity against human gastric cancer cell lines.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ivan Mosiagin, Anthony J. Fernandes, Alena Budinska, Liana Hayriyan, Kai E. O. Ylijoki, Dmitry Katayev
Summary: This study reports an efficient, mild, and catalytic ipso-nitration method of organotrimethylsilanes using an electrophilic N-nitrosaccharin reagent. The method allows chemo-selective nitration under mild reaction conditions and exhibits remarkable substrate generality and functional group compatibility. The reaction conditions are orthogonal to other common functionalities, allowing programming of molecular complexity via successive transformations or late-stage nitration. Detailed mechanistic investigation supports a classical electrophilic aromatic substitution mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Adrian Topolski
Summary: The paper presents a method to enhance the functionality of titanium alloy by covering the surfaces of titania nanotubes with platinum(II) bimetallic complexes and cisplatin. The modification process involves coating the nanotubes with (3-mercaptopropyl)triethoxysilane as a bridge between the nanotubes and platinum(II) coordination centers, and then applying platinum(II) dimethylformamide solutions to form homogenous layers of complexes bonded to the nanotubes substrate. The complexes and substrates were characterized using various spectroscopic and analytical techniques.
Article
Biochemistry & Molecular Biology
Luis R. Domingo, Maria Jose Aurell, Mar Rios-Gutierrez
Summary: The reaction between N-phenyl iminoborane and benzaldehyde, presented by Liu et al., was investigated using Molecular Electron Density Theory (MEDT). The formation of a fused aromatic compound involves three consecutive reactions: the formation of a weak molecular complex between the reactants, an intramolecular electrophilic attack of the activated carbonyl carbon, and a formal 1,3-hydrogen shift. This domino reaction shows similarities to the Bronsted acid catalyzed Povarov reaction.
Article
Chemistry, Multidisciplinary
Zhenwei Chu, Jinhua Li, Dafa Chen, Zhengyu Lu, Weiran Meng, Ming Luo, Haiping Xia
Summary: Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes. In this study, the formal [2+1] cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes were reported, offering a facile strategy for constructing tetracyclic conjugated compounds. The involvement of a metal vinylidene intermediate in the [2+1] cycloaddition was confirmed through deuterated experiments. Additionally, the electrophilic substitution reaction of the tetracyclic conjugated compound was investigated using density functional theory (DFT) calculated Fukui functions. These tetracyclic conjugated compounds exhibit broad absorption spectra in the whole visible region, making them potential photovoltaic materials.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tatsuki Okumi, Atsunori Mori, Kentaro Okano
Summary: A regiocontrolled halogen dance reaction of 2,5-dibromopyrroles is reported using an N,N-dimethylsulfamoyl group to facilitate the interconversion of 2,3- and 2,4-dibromopyrrolyllithiums. This method was successfully applied to the formal synthesis of atorvastatin.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yushin Shibuya, Koki Susami, Hiroyuki Fukuoka, Seiha Yamaoka, Kentaro Okano, Atsunori Mori
Summary: Chiraphos acts as a highly effective ligand for nickel catalysts in cross-coupling polymerization reactions. The efficient nickel(II) catalyst promotes the cross-coupling polymerization of 2,5-differently substituted 1,4-dihalobenzene, particularly with a sterically congested substituent at the side chain, resulting in the formation of poly(1,4-phenylene). This catalyst exhibits high activity and enables control over the molecular weight and degree of polymerization.
Article
Materials Science, Multidisciplinary
Sonoka Yamamoto, Ryutaro Yamashita, Chihiro Kubota, Kentaro Okano, Masatoshi Kitamura, Masahiro Funahashi, Syu-Cheng Ye, Yung-Tin Pan, Masaki Horie, Takuji Shintani, Hironori Murata, Hideto Matsuyama, Atsunori Mori
Summary: A thiophene-thiophene block copolymer with hydrophilic and hydrophobic side chains was synthesized. The block copolymer exhibited cylindrical microphase separation and the hydrophilic domain penetrated perpendicular to the substrate. The conductive properties of the thin film changed depending on its orientation to the substrate, with parallel orientation being conductive and perpendicular orientation being insulative. Electrochemical analysis showed that lithium ions transferred through the cylindrical domain composed of benzene sulfonic acid side chains.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Physical
Mizuho Yamagishi, Shohei Horike, Yasuko Koshiba, Atsunori Mori, Kenji Ishida
Summary: Broadband absorption and light-energy transfer in a pi-conjugated dendrimer, Ph-(7T)(3), were studied. The highly branched Ph-(7T)(3) macromolecule exhibited broadband absorption due to multiple pi-conjugations. The excited-state relaxation of the pi-conjugating system explained the light-energy transfer from the core to the thiophene dendrons.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Editorial Material
Chemistry, Organic
Munetaka Akita, Paola Ceroni, Corey R. J. Stephenson, Geiraldine Masson
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Kentaro Okano, Yuya Okui, Atsunori Mori
Summary: A formal synthesis of dictyodendrin B was achieved by regiocontrolled functionalization of the alpha,beta-dibromopyrrole derivative, followed by reductive cyclization and further chemical transformation. The synthesis involved the construction of the characteristic tetracyclic pyrrolo[2,3c]carbazole skeleton and manipulation of the ester moiety.
Article
Chemistry, Organic
Yuxuan Feng, Taro Yukioka, Mei Matsuyama, Atsunori Mori, Kentaro Okano
Summary: A method for the regioselective functionalization of haloarenes through deprotonative lithiation is described. The haloaryllithiums generated were trapped with a zinc chloride diamine complex in a batch reactor, resulting in the formation of organozinc species without aryne formation. These species reacted with electrophiles to yield the corresponding products in yields of 38-98%. The method was successfully applied to the gram-scale, five-step total synthesis of carbazomycin A with an overall yield of 33%.
Article
Chemistry, Organic
Masahiro Hosoya, Atsunori Mori, Kentaro Okano
Summary: The regioselectivity for deprotonation of a pyridylthiophene can be controlled by changing the reaction conditions. In addition, the in situ transmetalation and halogen dance on the corresponding organometallic species can be controlled by additives, reaction temperature, and the above reaction conditions. As a result, this method enables the synthesis of four iodinated constitutional isomers from a single starting material, 2-(5-bromo-2-thienyl)pyridine.
Article
Chemistry, Organic
Seiha Yamaoka, Hiroyuki Fukuoka, Naoki Noda, Kentaro Okano, Masaki Horie, Atsunori Mori
Summary: A nickel thiocyanate complex was synthesized and used as a catalyst for various polymerization reactions and coupling reactions. The polymerization of 1,4-dihalobenzenes and 2-halo-3-hexylthiophenes resulted in the formation of poly-1,4-phenylenes and poly(3-hexylthiophene-2,5-diyl), respectively. The complex also catalyzed Suzuki-Miyaura couplings and Buchwald-Hartwig aminations, leading to the formation of biaryls and arylamines.
Article
Chemistry, Multidisciplinary
Yuya Tanaka, Yeana Bae, Fumiya Ogasawara, Keita Suzuki, Shuji Kobayashi, Satoshi Kaneko, Shintaro Fujii, Tomoaki Nishino, Munetaka Akita
Summary: Precise control of molecule-electrode interface is achieved by designing ruthenium acetylide molecular wires with long-legged phosphine ligands, allowing for sterically controlled molecule-electrode interface. The observation of sharpened Raman signals for acetylene stretching in the self-assembled monolayers suggests the formation of uniform SAMs due to steric hindrance. Scanning tunneling microscope break-junction study reveals narrow conductance features, indicating a uniform molecular junction and effective electronic interactions unique to the long-legged derivatives.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Organic
Kengo Inoue, Atsunori Mori, Kentaro Okano
Summary: A two-step halogen transfer reaction of bromoarenes was reported. Bromoaryllithiums generated through deprotonative lithiation were converted into organozinc species by in situ zincation, followed by bromination to produce bromoarenes. It was also discovered that the bromo group could undergo regioselective translocation in the presence of ethylmagnesium chloride.
Article
Chemistry, Physical
Kohei Hosokawa, Kohei Tabuchi, Yuki Nakanishi, Kentaro Okano, Masaki Horie, Atsunori Mori
Summary: Multiple ring-closing metathesis of oligomeric bithiophene produced a vine-shaped oligomer with molecular asymmetry. Stereochemical studies revealed that the dimeric meso and racemic mixture converted to a meso-enriched product in the solid state, while the obtained meso compound reverted back to the meso and racemic mixture upon heating in chloroform solution. Heating the meso isomer in the solid state did not lead to isomerization.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Article
Chemistry, Organic
Kengo Inoue, Atsunori Mori, Kentaro Okano
Summary: A two-step halogen transfer method for bromoarenes was reported. By utilizing deprotonative lithiation and in situ zincation, organozinc species were generated and then subjected to bromination to obtain di-, tri-, and tetrabromoarenes with high yields. Regioselective bromine-magnesium exchange followed by electrophilic trapping resulted in benzene, pyridine, quinoline, pyrimidine, and thiazole derivatives with bromo group translocation.
Article
Polymer Science
Takuya Matsumoto, Masaki Kashimoto, Chihiro Kubota, Shohei Horike, Kenji Ishida, Atsunori Mori, Takashi Nishino
Summary: By controlling the cross-linking points and introducing cyclic siloxane side chains into the thiophene copolymer, the performance and flexibility of the polymer network were improved.
Article
Chemistry, Multidisciplinary
Yuya Tanaka, Hiroki Takahashi, Munetaka Akita
Summary: Understanding the electronic properties of mixed-valence states of organometallic molecular wires is crucial for studying electron transfer phenomena. In this study, diruthenium bridging wires with acyl-substituted cyclopentadienyl rings were synthesized and their properties were investigated. It was found that the interaction between the two metal centers is stronger in the para-isomers than in the meta-isomers. The spectroelectrochemical study showed significant higher-energy shifts of the (C O) vibrations upon oxidation, and the electron transfer rate constants were determined to be in the orders of 10(12) s-1 (para-isomers) and 10(9) s-1 (meta-isomers).
ACS ORGANIC & INORGANIC AU
(2022)
