Article
Chemistry, Multidisciplinary
Zhi-Bo Yan, Meng Peng, Qi-Long Chen, Ka Lu, Yong-Qiang Tu, Kun-Long Dai, Fu-Min Zhang, Xiao-Ming Zhang
Summary: This study presents a versatile silylation reaction using a SNIr catalyst to obtain heteroarylsilanes from heteroaryl C-H bonds. Mechanistic experiments reveal that favorable silylations occur at the γ or δ positions of chelating heteroatoms forming cyclic intermediates.
Article
Chemistry, Multidisciplinary
Shuai Liu, Frederic Robert, Yannick Landais
Summary: Dual Ni and Ir catalysis allows the efficient synthesis of arylsilanes containing a (TMS)(3)Si substituent from aryl bromides and (TMS)(3)SiH. Visible-light irradiation at 30 degrees C is used, avoiding the need for strong bases and high temperatures. The reaction proceeds through the generation of a silyl radical via hydrogen atom abstraction by a bromide radical.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Bin Li, Pierre H. Dixneuf
Summary: Metal-catalyzed silylation reactions play a crucial role in the synthesis of organometallic compounds, especially in the activation of sp(3)C-H bonds. By utilizing different metal catalysts, intermolecular and intramolecular sp(3)C-H bond silylations directed by nitrogen-containing heterocycles or amide functions can be achieved for the formation of stable organometallic species.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Organic
Mimi Xing, Huanhuan Cui, Chun Zhang
Summary: A novel nickel-catalyzed reductive cross-coupling method has been developed for constructing C-Si bonds under mild reaction conditions, allowing for the synthesis of structurally diverse organosilanes without Ni-catalyzed isomerization. The utility of this chemistry is demonstrated through further transformations of the product, while the radical mechanism of the reaction is elucidated through control experiments.
Article
Chemistry, Multidisciplinary
Shuai Liu, Frederic Robert, Yannick Landais
Summary: Dual Ni and Ir catalysis allows the visible-light-assisted synthesis of arylsilanes without the need for strong bases, high temperature, and air/moisture sensitive reagents, resulting in moderate to good yields.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Naofumi Hara, Nao Uemura, Yoshiaki Nakao
Summary: A C2-selective mono-silylation of various pyridines has been developed using a Rh-Al complex, where the site- and mono-selectivity are controlled by the coordination of pyridine to the Lewis-acidic Al center. A reaction mechanism is proposed based on the isolation of a (2-pyridyl)silylrhodium intermediate from several mechanistic studies.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Andres Arribas, Martin Calvelo, David F. Fernandez, Catarina A. B. Rodrigues, Jose L. Mascarenas, Fernando Lopez
Summary: The study presents a versatile and highly enantioselective intramolecular hydrocarbonation reaction for the synthesis of heteropolycyclic systems with chiral quaternary carbon stereocenters. The method relies on an iridium-(I)/bisphosphine chiral catalyst, yielding fused indole and pyrrole products with high enantiomeric excesses. DFT computational studies provided a detailed mechanistic profile and identified weak non-covalent interactions as key factors controlling the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Romane Manguin, Maria Galiana-Cameo, Tanakorn Kittikool, Cecile Barthes, Jompol Thongpaen, Etienne Bancal, Sonia Mallet-Ladeira, Sirilata Yotphan, Ricardo Castarlenas, Marc Mauduit, Jean-Baptiste Sortais, Olivier Basle
Summary: This article discusses the synthesis and characterization of a new series of iridium complexes with NHC-carboxylate ligands, which exhibit efficient catalytic activities in dehydrogenative directed C-H silylation of arenes, with excellent ortho-selectivity control.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Baptiste Neil, Lamine Saadi, Louis Fensterbank, Clement Chauvier
Summary: Benzylsilanes are widely used as stable synthetic intermediates in organic synthesis, but are mainly produced by stoichiometric procedures. Catalytic alternatives for silylation of benzylic C(sp(3))-H bonds are scarce due to the need for specialized directing groups and catalytic systems to compete with the kinetically-favored silylation of C(sp(2))-H bonds. In this study, we report the first general and catalytic-in-metal undirected silylation of benzylic C(sp(3))-H bonds under ambient, transition metal-free conditions using stable tert-butyl-substituted silyldiazenes (tBu-N=N-SiR3) as silicon source. The high activity and selectivity of the catalytic system is attributed to the facile generation of organopotassium reagents, including tert-butylpotassium.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zhuo Wu, Zechen Wu, Xueliang Sun, Weixin Qi, Zhengyang Zhang, Yanghui Zhang
Summary: The study presents a Pd-catalyzed intramolecular coupling of inert C(sp(3))-H and C(sp(2))-H bonds, leading to the formation of organic compounds.
Review
Multidisciplinary Sciences
Mirja Md Mahamudul Hassan, Saikat Guria, Sayan Dey, Jaitri Das, Buddhadeb Chattopadhyay
Summary: Transition metal-catalyzed C-H bond activation and borylation is a powerful synthetic method for transforming organoboron compounds to various functional groups. Remote C-H borylation is more challenging than ortho-borylation due to the inaccessibility of the C-H bonds. Recent discoveries in catalyst/ligand design, such as steric effects and noncovalent interactions, have enabled remote C-H borylation and its application in natural product synthesis. Ir-catalyzed C-H borylation is currently predominant, but cobalt catalysts are also being explored for sustainable and cost-effective development.
Article
Chemistry, Applied
Keita Anoyama, Gen Onodera, Tsutomu Fukuda, Masanari Kimura
Summary: An iridium-catalyzed ortho-C-H silylation of 2-arylpyridine derivative with hydrosilane by using phosphine-borane ligand has been developed. This reaction yields mono- and disilylated products in 81-99% yields, using various 2-arylpyridines. The length of the linkage between phosphorus and boron is crucial for the reaction to proceed.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Hyune-Jea Lee, Changmo Kwak, Dong-Pyo Kim, Heejin Kim
Summary: In this study, an atom-economic flow approach was developed for the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanes using serial organolithium reactions catalyzed by earth-abundant metal compounds. The use of t-BuOK as a catalyst enabled rapid reactions of organolithiums with hydrosilanes, leading to efficient generation of functionalized organolithiums and their consecutive reactions with hydrosilanes under mild conditions. The integrated one-flow system allowed for precise reaction control and combinatorial functionalizations of trihydrosilane, providing various tetrasubstituted organosilane libraries.
Article
Chemistry, Organic
Tianhao Xu, Wenhui Li, Kang Zhang, Yuhui Han, Long Liu, Tianzeng Huang, Chunya Li, Zhi Tang, Tieqiao Chen
Summary: The direct decarbonylative cyanation of benzoic acids with TMSCN was achieved through palladium catalysis. A wide range of nitriles, including those with functional groups, were synthesized in good to high yields. Moreover, this reaction was successfully applied to modifying bioactive molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Shrikant M. Khake, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports a branch-selective C-H alkenylation method using an iridium catalyst with alkenes, suitable for aniline derivatives containing a pyrimidine-directing group, offering a broad substrate scope and tolerating various functional groups. The origin of branch selectivity was investigated using density functional theory calculations.
Article
Chemistry, Multidisciplinary
Mingoo Jin, Rempei Ando, Marcus J. Jellen, Miguel A. Garcia-Garibay, Hajime Ito
Summary: The study introduces a novel design of emission crystalline molecular rotors with the ability to rotate elements based on the type of implanted metal. The activation energy for rotation can be tuned by changing the metal, impacting the energy barrier and electronic stabilization during rotational motion. The design provides a platform for manipulation of rotary dynamics and solid-state emission in crystalline molecular materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Keiichi Hayama, Rikuro Takahashi, Koji Kubota, Hajime Ito
Summary: Silylative dearomatizations of indole-2-carboxylates were achieved using a copper(I) catalyst and silylboronates, showing regioselective addition of silylcopper(I) species to indole substrates followed by diastereoselective protonation. The study also presented the first silylative dearomatization of pyrroles with the developed catalytic system.
Article
Chemistry, Physical
Koji Kubota, Daiyo Miura, Takumi Takeuchi, Shun Osaki, Hajime Ito
Summary: The study introduces a novel catalytic enantioselective nucleophilic borylation reaction of ketimines, leading to the efficient synthesis of optically active alpha-amino tertiary boronates with high enantioselectivity. The products can be further converted into peptidylboronic acid derivatives that are difficult to synthesize by other methods. Density functional theory calculations suggest that noncovalent interactions play a crucial role in determining the enantioselectivity of this reaction.
Article
Chemistry, Multidisciplinary
Koji Kubota, Tsubura Endo, Minami Uesugi, Yuta Hayashi, Hajime Ito
Summary: The study presents a palladium-catalyzed solid-state C-N cross-coupling of carbazoles with aryl halides via a high-temperature ball-milling technique, allowing for the efficient synthesis of N-arylcarbazole derivatives without the use of large amounts of organic solvents. Importantly, this method enables the coupling of poorly soluble aryl halides with large polyaromatic structures that are barely reactive under conventional solution-based conditions.
Article
Chemistry, Inorganic & Nuclear
Mingoo Jin, Rempei Ando, Hajime Ito
Summary: One-dimensional cationic coordination polymers can construct helical structures with different folding modes by diverse coordination geometries, leading to a change in emission wavelength in luminescent crystals.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Koji Kubota, Keisuke Kondo, Tamae Seo, Hajime Ito
Summary: This study investigates the unique reactivity of solid-state substrates and the effect of reaction temperature on the reaction rate. The results show that solid-state substrates with high melting points exhibit low reactivity, but the reaction rate can be accelerated by increasing the reaction temperature.
Article
Chemistry, Multidisciplinary
Yunpeng Gao, Chi Feng, Tamae Seo, Koji Kubota, Hajime Ito
Summary: The study demonstrates the efficient palladium-catalyzed Sonogashira coupling of solid aryl halides using high-temperature ball milling, resulting in a variety of materials-oriented polyaromatic alkynes and the synthesis of novel luminescent materials. The utility of this method is further exemplified by the rapid synthesis of a fluorescent metal-organic framework precursor, showcasing the potential of Sonogashira coupling for the preparation of functional materials.
Article
Multidisciplinary Sciences
Rina Takahashi, Anqi Hu, Pan Gao, Yunpeng Gao, Yadong Pang, Tamae Seo, Julong Jiang, Satoshi Maeda, Hikaru Takaya, Koji Kubota, Hajime Ito
Summary: This study presents a method for the general mechanochemical synthesis of magnesium-based carbon nucleophiles in air using a ball milling technique, which avoids the drawbacks of using dry organic solvents and long reaction times.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Rikuro Takahashi, Tamae Seo, Koji Kubota, Hajime Ito
Summary: The palladium-catalyzed cross-coupling under solid-state high temperature ball-milling conditions enables efficient construction of polyfluorinated structural motifs without the need for stoichiometric additives, large amounts of organic solvents, and exhibits a broad substrate scope.
Article
Chemistry, Physical
Mingoo Jin, Hajime Ito
Summary: This review summarizes the recent progress in stimuli-responsive mechanisms of Au(I) complexes, including crystal phase transitions and molecular rotation in crystalline media.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY C-PHOTOCHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Pan Gao, Julong Jiang, Satoshi Maeda, Koji Kubota, Hajime Ito
Summary: The use of calcium-based heavy Grignard reagents (R-CaX) in organic synthesis is not well-explored compared to conventional magnesium-based Grignard reagents (R-MgX). This is mainly due to the lack of a simple method to access organocalcium nucleophiles from readily available starting materials. In this study, the researchers demonstrate a mechanochemical technique using ball milling to generate calcium-based heavy Grignard reagents without complicated pre-activation processes. The method allows for the development of novel cross-electrophile-coupling reactions mediated by arylcalcium nucleophiles, which is difficult using conventional Grignard reagents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Koji Kubota, Emiru Baba, Tamae Seo, Tatsuo Ishiyama, Hajime Ito
Summary: This study presents the solid-state palladium-catalyzed cross-coupling between aryl halides and bis(pinacolato)diboron using ball milling. The reaction time is short and yields a variety of useful arylboronates in high yields. Importantly, the reactions can be conducted in air without the need for large amounts of dry and degassed organic solvents, highlighting the practicality of this method.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Natsuki Oyama, Sota Akiyama, Koji Kubota, Tsuneo Imamoto, Hajime Ito
Summary: Asymmetric gamma-boryl substitution of trifluoromethyl- and silyl-substituted alkenes using a copper(I) salt and optically active C-1 symmetric QuinoxP*-type bisphosphine ligand as the catalyst has been successfully demonstrated. The resulting products, silyl-substituted gem-difluoroallylboronates and chiral silyl- and difluoromethylene-containing homoallylic alcohols, exhibit high enantioselectivity and can further be transformed into structurally complex fluorinated chiral molecules with the silyl groups serving as cross-coupling sites.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hiroaki Iwamoto, Yu Ozawa, Yuta Hayashi, Tsuneo Imamoto, Hajime Ito
Summary: A new series of C-1-symmetric P-chirogenic bisphosphine ligands have been developed, which showed high performance in a copper(I)-catalyzed asymmetric borylation reaction. Computational studies highlighted the importance of the highly rigid phosphine conformation in achieving high stereo- and product-selectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Chi Feng, Tomohiro Seki, Shunichi Sakamoto, Toshiyuki Sasaki, Satoshi Takamizawa, Hajime Ito
Summary: This study discovered a reversible multi-stage shape-changing effect in a molecular crystal, where the shape changes and luminescence-color changes were induced by multi-step thermal phase transitions. The findings provide new strategies for imparting additional functionalities to known shape-memory materials.
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
