Review
Chemistry, Multidisciplinary
Naoto Chatani
Summary: The development of chelation-assisted C-H functionalization reactions has greatly contributed to the efficient utilization of C-H bonds. The use of precious metals as catalysts has been prevalent in these reactions. The Account described the development of Ni(0)- and Ni(II)-catalyzed chelation-assisted C-H functionalization reactions and their application in activating unreactive bonds.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Lin Li, Xin-Lian Liu, Jin-Yan Liang, Yong-Yu He, Ai-Jun Ma, Wei-Feng Wang, Jin-Bao Peng
Summary: A palladium-catalyzed dicarbonylation reaction of alpha-iodo-substituted ACPs has been developed for the synthesis of carbamoyl-substituted indenones. Two carbonyl groups are incorporated into the product by cleaving the proximal C-C bond of the ACPs. A broad range of carbamoyl-substituted indenones are efficiently prepared with good to excellent yields.
Article
Chemistry, Multidisciplinary
Qiang Zhang, Xiao Zou, Ningqi Zhang, Bo Liu
Summary: A novel cobalt-catalyzed protocol for the synthesis of carbinol derivatives and benzil derivatives has been developed. The corresponding arylated products were obtained from the addition of aryltrimethylgermanes to aromatic aldehydes and arylglyoxals in moderate to excellent yields under air atmosphere, using CoI2 as the catalyst and tmphen as the ligand.
Article
Chemistry, Organic
Jianlin Chun, Yukun Li, Xiaofei Xie, Kang Guo, Daoyuan Zhao, Kang Chen, Yingguang Zhu
Summary: This study develops a photoinduced copper-catalyzed method for the enantioconvergent remote alkynylation of N-hydroxyphthalimide esters via 1,4-heteroaryl migration. A broad range of heteroaryl-tethered chiral alkynes is synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species serves as both the photoredox and cross-coupling catalyst, providing a new platform for enantioconvergent remote alkynylations.
Article
Chemistry, Organic
Rajshekhar A. Unhale, Milon M. Sadhu, Vinod K. Singh
Summary: A novel organocatalytic asymmetric formal [3 + 2] cycloaddition has been developed for the synthesis of biologically relevant chiral spiroisoindolinone-indolines with excellent yields and enantioselectivity under mild conditions.
Article
Chemistry, Organic
Huihong Wang, Fei Cao, Weiwei Gao, Xiaodong Wang, Yuhang Yang, Tao Shi, Zhen Wang
Summary: Epoxides have been utilized as alkylating reagents in Pd(II)-catalyzed C-H alkylation and oxidative annulation to synthesize isoquinolones instead of isochromans. By modifying the reaction mechanism with the addition of oxidant and TEA, various isoquinolones have been successfully prepared with high yields up to 92%. This methodology has also been applied in the total syntheses of rupreschstyril, siamine, and cassiarin A in an efficient manner.
Article
Chemistry, Organic
Pinki Sihag, Masilamani Jeganmohan
Summary: A novel methodology for synthesizing diverse indanone compounds through a redox-neutral [4 + 1] annulation of unactivated alkenes with sulfoxonium ylides has been developed. The reaction is highly versatile and can accommodate various unactivated alkenes functionalized with sensitive functional groups as well as substituted sulfoxonium ylides. Additionally, multiple transformations such as ring-expansion, reduction, aldol condensation, and Wittig reaction can be carried out with the synthesized indanones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sudeshna Mondal, Ratnadeep Bera, Deepan Chowdhury, Suman Dana, Mahiuddin Baidya
Summary: An enol-assisted regioselective arene C-H alkylation with maleimides is developed under redox-neutral ruthenium-(II) catalysis, offering a wide variety of valuable 3-aryl succinimides including amino acid embedded frameworks in good to excellent yields. The products were also aromatized to produce synthetically useful resorcinol-based biaryls. Mechanistic studies support an organometallic pathway with a reversible C-H metalation step for this reaction.
Article
Chemistry, Organic
Lin Xiao, Xu-Ge Liu, Mei-Zhu Bao, Jia-Lin Song, Shao-Yong Chen, Yi-Chuan Zheng, Yan-Zhi Liu, Shang-Shi Zhang
Summary: The Cp*Rh(III)-catalyzed nitro-directed C-H alkylation/alkenylation of nitroarenes has been reported for the first time. This method exhibits high efficiency, broad substrate scope, and good functional group compatibility. Gram-scale experiments and synthetic applications confirmed the practicality of this method. Furthermore, preliminary mechanistic investigations consistently indicated that C-H bond cleavage is the rate-limiting step.
Article
Chemistry, Organic
Jiamin Wu, Jinli Zhang, Yongjuan Jiao, Gongtao Deng, Yingmei Li, Zhengyu Zhang, Yaojia Jiang
Summary: A unique decarbonylation of an amino acid derivative catalytic system has been developed via palladium-catalyzed C-C bond and C-N bond dual activations. This approach provides a straightforward avenue for constructing diverse functionalized amide compounds in good to excellent yields. The proposed reaction pathway may involve C-C bond and C-N bond dual activations based on mechanistic studies.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Junya Kitano, Yuji Nishii, Masahiro Miura
Summary: In this study, we report a novel synthesis method that achieves selective construction of C4-substituted benzofurans through a Rh-catalyzed reaction. This method avoids cumbersome multistep processes and has high synthetic efficiency.
Article
Chemistry, Organic
Vijaykumar H. Thorat, Hasil Aman, Yu-Lin Tsai, Gangaram Pallikonda, Gary Jing Chuang, Jen-Chieh Hsieh
Summary: This study explores the co-catalyzed reactions of 2-halobenzamides and alkynes to form isoquinolones or 2-vinyl benzamides, with the formation of selective products controlled by ligands. The mechanism study reveals that these reactions proceed through different pathways, involving radical processes and two-electron transfer activation of the C-X bond.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Jian Tang, Fengjie Lu, Xinyi Zhang, Yiming Su, Ensheng Zhang, Zhiyu Yang
Summary: Efficient synthesis of phenylalanine-derived oxazoles and imidazolidones can be achieved through directed copper-catalyzed reactions involving selective C-O or C-N coupling. This strategy utilizes inexpensive commercial copper catalysts and readily available starting materials, offering a convenient and reliable approach for the assembly of versatile heterocyclic building blocks.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhi-Jian Han, Ze-Xuan Zhang, Jin-Jin Lin, Bin Ma, Lu-Xi Yang, Wei-Gao Pu, Yu-Min Li, Hao Chen, Chao-Shan Da
Summary: This work demonstrates the high-yield synthesis of pyrano[4,3-c]pyridine-1,5(6H)-diones via Rh(III)-catalyzed dual C(sp2)-H functionalization and C-O/C-N annulation. The substrates used, monoamide fumarates and acetylenes, are simple, readily available, and inexpensive. The addition of AgSbF6 effectively improves the yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Demao Chen, Changfeng Wan, Yunyun Liu, Jie-Ping Wan
Summary: A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been developed via the reactions of enaminones, hydrazine hydrochloride, and internal alkynes using Rh catalysis. The cascade reactions demonstrate the remarkable high-order bond functionalization, involving the transformation of aryl C-H, ketone C=O, and alkenyl C-N bonds in the enaminones. This study highlights the individual advantage of enaminones in the design of novel and efficient synthetic methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Amrita Das, Naoto Chatani
Summary: The Rh(i)-catalysed imine-directed oxidative [3 + 2] cycloaddition of benzylamines with maleimides is reported, which can use a wide range of both substrates and achieve a successful one-pot three component strategy. Mechanistic studies suggest the formation of a zwitterionic intermediate through Rh-mediated activation of a benzylic C(sp(3))-H bond of the imine.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yusuke Ano, Masaya Higashino, Yuki Yamada, Naoto Chatani
Summary: The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is crucial for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones can be applied to this transformation, yielding aryl or alkenyl nitriles, respectively.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Attila Taborosi, Oiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori
Summary: The reaction of N-8-amino-quinolinyl aromatic amides with maleimides under rhodium(I) catalysis results in C-H alkylation at the ortho position of the amide. Computational studies using density functional theory (DFT) have shown that the reaction proceeds through several steps including NH amide deprotonation, oxidative addition, migratory insertion, reductive elimination, and protonation. The oxidation number of the Rh catalyst plays a crucial role in determining the reaction path.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ken Yamazaki, Supriya Rej, Yusuke Ano, Naoto Chatani
Summary: In this study, the mechanism of the metal-free ortho C-H borylation of benzaldehyde derivatives using a transient imine directing group was extensively investigated using DFT calculations. It was proposed that the experimentally observed reactivity enhancement may originate from the tunability of the destabilizing strain energies.
Article
Chemistry, Physical
Qiyuan He, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports the palladium-catalyzed reaction of 2-methylbenzamides with acrylic esters, resulting in the production of isoquinolinones. The reaction selectively occurs at the ortho methyl C-H bond via a six-membered palladacycle, rather than at the ortho C-H bond via a five-membered palladacycle. The key to the success of the reaction is the use of maleic anhydride as a ligand. Computational analyses indicate that the coordination of the maleic anhydride ligand greatly stabilizes the transition state for beta-hydride elimination and accelerates the reaction rate.
Article
Chemistry, Physical
Shrikant M. Khake, Naoto Chatani
Summary: The Rh(III)-catalyzed C-H oxidative alkylation of aniline derivatives with readily available secondary allyl alcohols is described. The reaction exhibited tolerance towards various functional groups. Different oxidants are required depending on the structure of the allyl alcohol. Mechanistic experiments revealed insights into the catalyst regeneration step.
Review
Chemistry, Multidisciplinary
Supriya Rej, Naoto Chatani
Summary: Considerable advances have been made in the field of C-H functionalization, with special interest in C-H borylation due to its wide applications. Transition-metal-catalyzed regioselective strategies have been developed, but the use of precious metals and contamination by metal precursors limit their application in large-scale synthesis. Recent trends involve the use of transition-metal-free systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Bernard F. Parker, Naoto Chatani
Summary: Selective hydrodefluorination of amides at the ortho position is achieved using sodium borohydride and a nickel catalyst under mild conditions. The formation of a specific nickelacycle intermediate allows for selectivity without the need for electronic directing groups, while fluorine atoms in other positions remain intact. This method eliminates the use of stoichiometric silanes commonly used in other defluorination reactions, resulting in minimal organic waste byproducts.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sanjit K. Mahato, Naoto Chatani
Summary: This study reports the Ir(III)-catalyzed ortho C-H amidation of 2-aroylimidazoles with 3-aryldioxazolones as an amidating reagent. The method demonstrates a wide substrate scope and compatibility with various functional groups. Mechanistic studies reveal that the cleavage of C-H bond is reversible and not the rate-determining step. The presence of an electron-donating group in 2-aroylimidazoles and an electron-withdrawing group in 3-aryldioxazolones significantly accelerates the reaction, suggesting that nitrene insertion is the rate-determining step.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Yusuke Ano, Daichi Takahashi, Yuki Yamada, Naoto Chatani
Summary: The palladium-catalyzed skeletal rearrangement of 3-arylcyclobutanones into 1-indanones is achieved using a Pd(0)/IMes catalyst. The reaction occurs via cleavage of C(carbonyl)-C(sp3) and C(sp2)-H bonds, without the need for an extra reactive functional group or a directing group. Deuterium-labeling experiments indicate that the C-C bond activation is the initial step, followed by rate-determining C-H activation.
Article
Chemistry, Organic
Yusuke Ano, Sakura Takahashi, Naoto Chatani
Summary: The palladium-catalyzed reaction of alkyl 2-vinylbenzoates with silyl-protected alkynyl bromides selectively produces 3-alkynylated isochroman-1-ones. The use of an alkyl ester group as an effective oxygen nucleophile is crucial for the efficient 1,1-alkynyloxygenation of alkenes.
Review
Chemistry, Multidisciplinary
Naoto Chatani
Summary: The development of chelation-assisted C-H functionalization reactions has greatly contributed to the efficient utilization of C-H bonds. The use of precious metals as catalysts has been prevalent in these reactions. The Account described the development of Ni(0)- and Ni(II)-catalyzed chelation-assisted C-H functionalization reactions and their application in activating unreactive bonds.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Rie Yoshimoto, Attila Taborosi, Qiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori
Summary: The reaction between aromatic amides and maleimides, catalyzed by palladium, leads to the formation of a product with double C-H bond activation, occurring at both the benzylic and meta positions. Computational chemistry studies reveal a stepwise mechanism involving a six-membered palladacycle, maleimide insertion, protonation of the Pd-N bond, and activation of the meta C-H bond. The site selectivity is determined by the interaction energy controlling the insertion of maleimide into the Pd-C(sp(3)) bond. The meta C-H bond activation step is identified as the rate-determining step based on the energetic span model. The 2-thiomethylphenyl group is found to function effectively as a directing group due to strong Pd-S bonding and the destabilizing effect of the deformation energy.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Takuya Igarashi, Ryoma Shimazumi, Naoto Chatani, Mamoru Tobisu
Summary: In this study, the nickel-catalyzed methylation of arylphosphines using AlMe(3)via the cleavage of unactivated C(aryl)-P bonds was reported. This reaction enables the direct substitution of an aryl group on a phosphorus center with a methyl group. The catalytic methylation can occur when phosphine oxides and sulfides are used as substrates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Aymen Skhiri, Attila Taborosi, Nozomi Ohara, Yusuke Ano, Seiji Mori, Naoto Chatani
Summary: A rhodium(I)-catalysed reaction was conducted using aromatic amides containing a 2-(methylthio)aniline directing group and maleimides, resulting in the formation of isoindolone spirosuccinimides under aerobic, metal oxidant-free, and solvent-free conditions. The use of a (2-methylthio)aniline directing group led to C-H oxidative alkenylation/cyclization, in contrast to a previous study with an 8-aminoquinoline directing group. Analysis using density functional theory (DFT) calculations identified the main steps involved in the reaction mechanism, including oxidative addition/migratory insertion and C-N bond formation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Alexander M. Prophet, Kritanjan Polley, Gary J. Van Berkel, David T. Limmer, Kevin R. Wilson
Summary: The oxidation kinetics of iodide by ozone at the air-water interface is studied in single microdroplets. Molecular simulations and kinetic modeling are used to understand the underlying multiphase mechanism.
Article
Chemistry, Multidisciplinary
Rong Zhang, Jiajing Lan, Fei Wang, Shumei Chen, Jian Zhang
Summary: By utilizing 1,1'-ferrocene dicarboxylic acid as a chelating and surface protection ligand, we have synthesized multi-nuclear indium oxide clusters with varying nuclear sizes, including heptanuclear and thirteen-nuclear clusters. These clusters possess labile coordination sites, allowing for structural modification and self-assembly, resulting in the formation of various cluster structures.
Article
Chemistry, Multidisciplinary
Hui Wang, Hui Liu, Mingsen Wang, Jiaheng Hou, Yongjun Li, Yuancheng Wang, Yingjie Zhao
Summary: Two supramolecular complexes were prepared using CBs and M1, and their single-crystal structures were analyzed by SCXRD. The unexpected 1:2 self-assembly structure between M1 and CB[8] was discovered for the first time. These complexes exhibit unique photophysical properties and provide valuable information about the structure and photophysical properties of supramolecular complexes.
Article
Chemistry, Multidisciplinary
Chang-Hee Lee, Sookil Park, Sanggil Kim, Ji Young Hyun, Hyun Soo Lee, Injae Shin
Summary: The epidermal growth factor receptor (EGFR) is a cell-surface glycoprotein involved in cell proliferation and tumor development. This study used a fluorescently labeled EGFR to investigate its time-dependent endocytosis in live cells and found that appended glycans affect EGFR internalization. Additionally, the study detected sialic acid residues attached to EGFR on the live cell surface using FRET-based imaging. This research provides valuable insights into the cellular functions of EGFR.
Article
Chemistry, Multidisciplinary
Subhankar Sahu, Lokesh Kumar, Sumita Das, Dipti Gupta, Ruchi Anand
Summary: This study proposes a strategy that combines organic electronics with biosensor scaffolds to create a compact device for monitoring environmental aromatic pollution. By coupling biosensing protein MopR with an organic electrochemical transistor (OECT), a sensor module capable of efficient detection of phenol was designed. Exclusive phenol detection with minimal loss of sensitivity could be achieved in complex pollutant mixtures and real environmental samples.
Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Multidisciplinary
Yueci Wu, Lu-Lu Sun, Hai-Hao Han, Xiao-Peng He, Weiguo Cao, Tony D. James
Summary: Drug-induced liver injury (DILI) is a common cause of acute liver failure in the USA and Europe, but most cases can be recovered or prevented by discontinuing the offending drug. Recent research has found that peroxynitrite (ONOO-) can be used as a potential indicator for early diagnosis of DILI, and there is an urgent need to establish a method to detect and track peroxynitrite in DILI cases. In this study, a FRET-based nano fluorescent probe CD-N-I was developed, which showed high selectivity and sensitivity in detecting peroxynitrite. The probe successfully detected exogenous peroxynitrite in live cells and endogenous peroxynitrite in APAP-induced liver injury of HepG2 cells.
Article
Chemistry, Multidisciplinary
Dmitry L. Lipilin, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman
Summary: This article describes a direct photocatalytic method for the thiolation of unprotected acids, which was previously challenging. By using a thionocarbonate reagent with an N-O bond, the efficient conversion of carboxylic acids to thiols is achieved.
Article
Chemistry, Multidisciplinary
Jason Malenfant, Lucille Kuster, Yohann Gagne, Kouassi Signo, Maxime Denis, Sylvain Canesi, Mathieu Frenette
Summary: Raman microscopy can reveal compound-specific vibrational fingerprints without sample preparation. The combination of efficient theoretical calculations and a user-friendly software can accurately predict peak positions and provide match scores to assist with structure determination.
Article
Chemistry, Multidisciplinary
Jayoh A. Hernandez, Paul S. Micus, Sean Alec Lois Sunga, Luca Mazzei, Stefano Ciurli, Gabriele Meloni
Summary: Essential trace metals play crucial roles in the survival and virulence of bacterial pathogens. Helicobacter pylori requires nickel for colonization and persistence in the stomach, and NixA is an essential nickel transporter in this process. This study characterizes the selectivity and electrogenic nature of NixA-mediated nickel transport.
Article
Chemistry, Multidisciplinary
Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.
Article
Chemistry, Multidisciplinary
Jacqueline R. Santhouse, Jeremy M. G. Leung, Lillian T. Chong, W. Seth Horne
Summary: By studying the folding kinetics and mechanism of the BdpA sequence, researchers found that altering the backbone connectivity can affect protein folding. This suggests that protein mimetic chains have a significant degree of plasticity in transitioning between unfolded and folded states.
Article
Chemistry, Multidisciplinary
Divanshu Gupta, Ralf Einholz, Holger F. Bettinger
Summary: This study presents the first direct spectroscopic evidence of a cyclic seven-membered iminoborane. Compared to linear amino-iminoboranes, this cyclic iminoborane exhibits weakened bond strength and lower Lewis acidity value. The study suggests that the reduced ring strain of cyclic iminoborane prevents nitrogen fixation but allows facile (2 + 2) cycloaddition reaction with C2H4.
Article
Chemistry, Multidisciplinary
Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas
Summary: This study reveals the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI) using a synergistic approach that combines 3D ED, ssNMR, and DFT techniques. By overcoming these challenges, this methodology opens up new avenues for material characterization, driving exciting advancements in the field.
