Article
Chemistry, Multidisciplinary
Grace A. Lutovsky, Samuel N. Gockel, Mark W. Bundesmann, Scott W. Bagley, Tehshik P. Yoon
Summary: In this study, a direct decarboxylative cross-coupling of native carboxylic acids with nucleophilic coupling partners mediated by inexpensive and non-toxic Fe(III) salts was reported. This method involves an initial photochemical decarboxylation followed by radical-polar crossover, enabling the construction of diverse carbon-carbon, carbon-oxygen, and carbon-nitrogen bonds with remarkable generality.
Article
Chemistry, Physical
K. Hiba, G. Anjali Krishna, S. Prathapan, K. Sreekumar
Summary: The palladium incorporated amine-functionalized dendronized polymer showed high palladium content and selectivity in Heck coupling reaction, with products in trans configuration. The catalyst exhibited stability, high catalytic activity and remarkable stereoselectivity, making it a promising candidate for further studies on potential antitubercular activity.
Article
Chemistry, Organic
Tomotoki Matsuo, Kazunori Nagao, Hirohisa Ohmiya
Summary: In this study, a visible light-mediated organophotoredox catalysis was developed for the cross-coupling between aliphatic carboxylic acid-derived redox active esters and organosilanes. This protocol enables the formation of C(sp3)-C(sp3), C(sp3)-C(sp2), and C(sp3)-C(sp) bonds under transition-metal free and mild reaction conditions. Additionally, the radical relay-type dicarbofunctionalization of styrene derivatives using organosilanes and aliphatic redox active esters was demonstrated.
TETRAHEDRON LETTERS
(2022)
Article
Multidisciplinary Sciences
Kwiyong Kim, Alexandra Zagalskaya, Jing Lian Ng, Jaeyoung Hong, Vitaly Alexandrov, Tuan Anh Pham, Xiao Su
Summary: In this study, a bifunctional redox-electrode was designed to achieve the reactive separation of nitrate to ammonium in a single electrochemical cell, providing an attractive solution for pollutant remediation and ammonia production. The results show that electrochemical control can achieve reversible nitrate uptake greater than 70 mg/g and greatly enhance energy efficiency. This study provides a generalized strategy for a fully electrified reaction-separation pathway for modular nitrate remediation and ammonia production.
NATURE COMMUNICATIONS
(2023)
Article
Polymer Science
Sung Hyun Cho, Ho-Joong Kim, Dong-Hyun Lee, Si Kyung Yang
Summary: A new class of dendronized polymers with both polyglycerol dendrons (PGDs) along the backbone and polylysine dendrons (PLDs) on the side-chains has been synthesized. The resulting doubly dendronized polymers have multiple amine and hydroxyl groups on the surfaces, which can be used for incorporating additional functionalities and making the structure water-soluble. These polymers can also be modified to generate positively charged groups for gene delivery applications.
Article
Biochemistry & Molecular Biology
Yan Ding, Xiacong Zhang, Wen Li, Afang Zhang
Summary: Thermoresponsive dendronized gelatins or gelatin methacrylates were used to efficiently reduce Au(III) and form stable gold nanoparticles through UV irradiation. The crowded OEG dendrons along the gelatin backbones create a hydrophobic microenvironment, promoting the reduction of Au(III) and stabilizing the formed AuNPs. This study presents a novel platform for environmentally friendly synthesis of noble metal nanoparticles and suggests a new strategy for developing smart nano-biosensors and nano-devices.
Article
Chemistry, Physical
Long Huang, Rajesh Kancherla, Magnus Rueping
Summary: The advent and development of photoredox/nickel synergistic catalysis have enabled the use of various alkyl radical precursors in the cross-coupling arylation and addressed the challenge of regiodivergent synthesis. We disclose a visible light nickel-catalyzed protocol for the deaminative cross-coupling of redox-active imines with various electrophiles, allowing for the rapid construction of C(sp(3)) enriched arene architectures in a regiodivergent manner.
Article
Chemistry, Physical
Xuchao Wang, Feipeng Liu, Zijuan Yan, Qing Qiang, Wei Huang, Zi-Qiang Rong
Summary: The study introduces a redox-neutral Ni-catalyzed cross-coupling reaction that converts two readily available precursors into ketones, which are important structural motifs in various biologically active compounds. By using a commercially available nickel/Triphos catalytic system, a wide range of easily accessible alkenyl primary alcohols and aryltriflates can be efficiently converted into ketones with good yields and functional group tolerance. This transformation also demonstrates its utility in late-stage functionalization of a large set of complex molecules to access more functionalized aromatic ketones.
Article
Chemistry, Multidisciplinary
Jinkyung Noh, Gregory I. Peterson, Tae-Lim Choi
Summary: The study investigated the mechanochemical degradation of bottlebrush and dendronized polymers in solution and solid states, revealing different backbone scission behaviors based on their elongated conformations in solution and arm architecture in solid state. The results suggest important implications for the development of new mechanoresponsive materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yi Yao, Ke Zhang, Jiachun Chen, Wen Li, Afang Zhang
Summary: The paper presents a method for the visible-light-triggered fabrication of monodispersed gold and silver alloy nanoparticles using dendronized chitosans. The resulting nanocomposites show promising photothermal properties and excellent catalytic activity.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Roman G. Belli, Victoria C. Tafuri, Matthew Joannou, Courtney C. Roberts
Summary: This study describes a redox-active ligand-enabled alkyl-alkyl cross-coupling method using a d(0) metal, which allows for controlled oxidative addition, prevents beta-hydride elimination, and tolerates hindered electrophiles.
Article
Polymer Science
Ya Qun Zou, Bowen Hu, Ling Chen, Tuo Ji, Ming Yang, Chang An Yang
Summary: This study focused on the synthesis and characterization of novel dual-stimulus responsive supramolecular dendronized copolymers, which exhibited excellent thermal- and pH-responsive properties. The copolymers were able to be stabilized at specific temperatures under different conditions and could be effectively regulated by adjusting the amino-to-aldehyde molar ratio. Additionally, these copolymers showed superior performance in encapsulation and release behavior of the Nile red fluorophore.
IRANIAN POLYMER JOURNAL
(2021)
Article
Chemistry, Organic
Tie-Gen Chen, Lucas Mele, Olivier Jentzer, Dominique Delbrayelle, Pierre-Georges Echeverria, Julien C. Vantourout, Phil S. Baran
Summary: A new approach using a radical retrosynthetic strategy to dissect the molecule into two halves is reported. By using reductive decarboxylative cross-coupling, a simple indoline can be coupled to a chiral pool-derived fragment to arrive at the target in only seven steps, avoiding the use of resolution strategies or asymmetric hydrogenation.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Weigang Zhang, Mengjun Huang, Zhenlei Zou, Zhengguang Wu, Shengyang Ni, Lingyu Kong, Youxuan Zheng, Yi Wang, Yi Pan
Summary: Redox-active benzimidazolium sulfonamides have been developed as thiolating reagents for reductive C-S bond coupling. The IMDN-SO2R reagent provides a stable cationic precursor to generate highly active N-S intermediates, enabling successful cross-electrophilic coupling with various organic halides. The use of an electrophilic sulfur source has practical benefits such as broad substrate scope and excellent tolerance, while avoiding catalyst deactivation and unpleasant odors from thiols.
Article
Chemistry, Organic
Kai Kang, Daniel J. Weix
Summary: This study successfully develops a two-step, one-pot protocol for the in situ generation of N-hydroxyphthalimide esters and their nickel-catalyzed cross-electrophile coupling with unactivated alkyl bromides, enabling the construction of C(sp3)-C(sp3) bonds. The conditions tolerate various functional groups, and mechanistic studies demonstrate the conversion of both substrates to alkyl radicals during the reaction.
Article
Chemistry, Multidisciplinary
Tatsuya Morofuji, Yu Matsui, Misa Ohno, Gun Ikarashi, Naokazu Kano
Summary: A photocatalytic Giese-type reaction using alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported, demonstrating the generation of various alkyl radicals and their trapping with electron-deficient olefins to yield desired products. The generation process of methyl radicals from methylsilicate with C,O-bidentate ligands was investigated using theoretical calculations, providing insights into their facile generation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Akihiro Shimizu, Yu Ishizaki, Shun Horiuchi, Takashi Hirose, Kenji Matsuda, Hiroyasu Sato, Jun-ichi Yoshida
Summary: The study focused on designing and synthesizing small pi-conjugated zwitterions with electron-donating anions and electron-accepting cations. By adjusting the energy difference and interplanar angle between the anion's HOMO and the cation's LUMO, the molecules exhibited small HOMO-LUMO energy gaps, showing amphoteric redox properties and near-infrared electronic absorption exceeding 1000 nm.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tatsuya Morofuji, Shota Nagai, Youhei Chitose, Manabu Abe, Naokazu Kano
Summary: This study reveals the crucial role of acid in the dearomative photocycloaddition of quinolines to olefins, enhancing the reactivity of quinolines' triplet state towards olefins.
Article
Chemistry, Organic
Tatsuya Morofuji, Kota Inagawa, Naokazu Kano
Summary: In this study, a method was developed to convert para-substituted pyridine rings into meta-dialkylamino-substituted benzene rings through sequential ring-opening and ring-closing reactions. This process can be considered as a hybrid of skeletal editing and C-H amination of pyridine rings.
Article
Chemistry, Organic
Ayane Kayama, Akihiro Shimizu, Ryo Shintani
Summary: The study describes the design and synthesis of a novel anthracene-based zwitterion with amphoteric redox properties and low-energy-light absorption. DFT calculations indicate that replacing C-H with N+-Me and introducing O- is essential for significantly altering the electronic structure and properties of anthracene.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Shinobu Arikawa, Akihiro Shimizu, Daisuke Shiomi, Kazunobu Sato, Ryo Shintani
Summary: By introducing bulky substituents onto the reactive zigzag edges, a kinetically stabilized crystalline form of triangulene was successfully synthesized and isolated for the first time, opening up new possibilities for the synthesis and isolation of other hydrocarbons with higher spin multiplicity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Tatsuki Yoshida, Yuki Honda, Tatsuya Morofuji, Naokazu Kano
Summary: This study developed a transition-metal-free oxidative C(sp(2))-C(sp(2) coupling of boronic acids and organolithiums using phenothiazinium ions. N-methylphenothiazine Soxide (PTZSO) was found to efficiently convert boronic acids to phenothiazinium ions, with insights into the unique reactivity of PTZSO gained from theoretical calculations and experiments.
Article
Chemistry, Multidisciplinary
Akihiro Shimizu, Tetsuya Morikoshi, Kenji Sugisaki, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Ryo Shintani
Summary: This study describes the design, synthesis, and isolation of a Kekule hydrocarbon with a triplet ground state. The triplet ground state was confirmed through ESR experiments, and the structure and fundamental physical properties were also revealed. The key aspect of the molecular design is the decrease in bonding interaction in the singlet state through aromatic stabilization of benzene rings and the increase of exchange interaction of unpaired electrons, which is favorable for the triplet state. These findings contribute to the development of hydrocarbon-based organic magnetic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Tatsuki Yoshida, Yuki Honda, Tatsuya Morofuji, Naokazu Kano
Summary: Here, we report a transition-metal-free O-arylation reaction of alcohols and phenols using S-arylphenothiaziniums, which can be easily synthesized from boronic acids. Aryl substituents derived from arylboronic acids were selectively introduced into the hydroxy groups in alcohols and phenols, resulting in the synthesis of various aryl ethers. The selectivity of this reaction is supported by theoretical calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Tatsuya Morofuji, Naokazu Kano
Summary: This article provides an overview of the progress in connecting sp2 carbons in chemical synthesis using ligand coupling on sulfur, and discusses the control of selectivity, expansion of the scope, and applications of the reaction.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Tatsuya Morofuji, Shota Nagai, Airi Watanabe, Kota Inagawa, Naokazu Kano
Summary: This study reports a new activation mode of amine catalysis called streptocyanine, which enables the conversion of pyridine rings to benzene rings. By N-arylation of pyridines with an alkenyl substituent at the 3-position, N-arylpyridiniums are generated, which can react with a catalytic amount of piperidine to form streptocyanine intermediates. These intermediates can then undergo a ring-closing reaction to form a benzene ring, releasing the amine catalyst. Mechanistic studies support the proposal that streptocyanine is an intermediated in this catalytic process.
Article
Chemistry, Multidisciplinary
Shinobu Arikawa, Akihiro Shimizu, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Hikaru Sotome, Hiroshi Miyasaka, Masahito Murai, Shigehiro Yamaguchi, Ryo Shintani
Summary: A kinetically-stabilized nitrogen-doped triangulene cation derivative with a triplet ground state that exhibits near-infrared emission has been synthesized and isolated. The triplet ground state with a large singlet-triplet energy gap was experimentally confirmed by magnetic measurements. The nitrogen-doped triangulene cation derivative is highly stable even in solution under air and exhibits near-infrared absorption and emission due to the broken alternancy symmetry of triangulene.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tatsuya Morofuji, Takuma Kurokawa, Youhei Chitose, Chihaya Adachi, Naokazu Kano
Summary: In this study, we propose a versatile organic photocatalyst, 4[Cz(CF3)(2)]IPN, which is capable of high oxidizing power electron-transfer-driven reactions and Ir photocatalyst energy-transfer-driven reactions. It showed good catalytic performance in radical reactions and dearomative cycloaddition reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Naokazu Kano, Nathan J. O'Brien, Kosuke Aoki, Yui Matsuda, Tatsuya Morofuji
Summary: The first phosphinoboronic ester with a fused bicyclic framework was successfully synthesized and characterized in this study. The crystal structure revealed a remarkably short P-B bond length, demonstrating the unique chemical properties of this compound.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Gun Ikarashi, Tatsuya Morofuji, Naokazu Kano
CHEMICAL COMMUNICATIONS
(2020)
