Article
Chemistry, Organic
Smruti Ranjan Mohanty, Namrata Prusty, Tanmayee Nanda, Shyam Kumar Banjare, Ponneri C. Ravikumar
Summary: In this study, the ruthenium-catalyzed regioselective sp2(C-H) monoalkenylation of N-arylpyridones was demonstrated, where the pyridone served as a weakly coordinating directing group. Importantly, this methodology was effectively applied to the synthesis of various drug analogues, with high yields up to 93%. HRMS analysis also revealed the presence of a six-membered ruthenium complex.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Ming Zeng, Jiaqi Chen, Fengye Li, Haojie Li, Lan Zhao, Dengzhao Jiang, Jun Dai, Wenbo Liu
Summary: 1,3,5-triazines, especially indole functionalized triazine derivatives, have shown excellent activities in anti-tumor, antibacterial, and anti-inflammatory fields. Traditional methods for synthesizing N-(2-triazine) indoles have limitations due to unstable materials and complex operations. In this study, an efficient ruthenium-catalyzed oxidative synthesis of N-(2-triazine) indoles by C-H activation was developed, resulting in moderate to good yields. The reaction proceeded through a proposed six-membered ruthenacycle intermediate, indicating the chelation assistance of the triazine ring in the formation of N-(2-triazine) indoles.
Article
Chemistry, Organic
Yaoguang Sheng, Jianmin Zhou, Yi Gao, Bingbing Duan, Yi Wang, Aleksandr Samorodov, Guang Liang, Qiuhua Zhao, Zengqiang Song
Summary: This study achieved the synthesis of 7-amido indoles via regioselective C-H bond functionalization under Ru(II) catalysis, with a wide range of applicable substrates and good conversion yields. Deuteration studies and control experiments were conducted to elucidate the mechanism of this transformation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Argha Saha, Srimanta Guin, Wajid Ali, Trisha Bhattacharya, Sheuli Sasmal, Nupur Goswami, Gaurav Prakash, Soumya Kumar Sinha, Hediyala B. Chandrashekar, Sanjib Panda, S. S. Anjana, Debabrata Maiti
Summary: The Fujiwara-Moritani reaction has made a significant contribution to contemporary C-H activation protocols. By establishing a photoredox catalytic system, the regioselective Fujiwara-Moritani reaction can be achieved through visible light without the need for silver salts and thermal energy. This sustainable protocol has importance in synthesizing natural products, chiral molecules, drugs, and diversifying functionalizations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Sagar D. Nale, Raju S. Thombal, Yong Rok Lee
Summary: A ruthenium(II)-catalyzed switchable ortho functionalization of 1-arylpyrazoles with maleimides has been developed, allowing for the selective installation of diverse succinimides and maleimides substituents on the aromatic ring of 1-arylpyrazoles via alkylation and alkenylation under acidic and basic conditions. This methodology features broad substrate scope, high functional group tolerance, selective functionalization, and superior reactivity.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jeong-Yu Son, Da-Hye Jeon, Haeun Jang, Phil Ho Lee
Summary: A method for the synthesis of a wide range of 1,2-benzothiazines bearing various functional groups has been developed using transition metal-catalyzed C-H activation reactions, providing efficient synthesis from readily available starting materials with broad substrate scope and good regioselectivity.
ISRAEL JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Sandip Kumar Gupta, Niranjan Panda
Summary: A Pd(II)-catalyzed dehydrogenative remote C4-H coupling of indoles with unfunctionalized arenes at room temperature was achieved using a weak chelating trifluoroacetyl group as a directing group. Various substituents on the arenes were compatible with the dehydrogenative cross coupling reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Krishna Kanta Das, Asim Kumar Ghosh, Alakananda Hajra
Summary: This study describes an Earth-abundant and water-tolerant manganese(I)-catalyzed alkenylation reaction via C-H bond activation with a unique level of E-selectivity. The reaction proceeds by controlling the C3 nucleophilicity of 2-aryl indazoles. This method is applicable to the late-stage functionalization of complex molecules.
Article
Chemistry, Organic
Biao Guo, Jiaying Lv, Le Lu, Ruimao Hua
Summary: A novel method for constructing the cyclopenta[c]quinoline ring has been developed, which involves the cyclization of 3-bromoindoles with internal alkynes in the presence of palladium. The mechanism of the formation of the cyclopenta[c]quinoline ring is proposed to proceed via a double [1,5] carbonsigmatropic rearrangement of the spirocyclic cyclopentadiene intermediate, generated from the cyclization of 3-bromoindoles with internal alkynes. This study also presents a new ring-expansion reaction of the pyrrole ring to pyridine via one carbon insertion into the C2-C3 bond of indoles, providing a simple and distinct route for constructing tricyclic fused-quinoline derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Bartlomiej Sadowski, Binbin Yuan, Zhipeng Lin, Lutz Ackermann
Summary: In this study, electrocatalytic peri C-H alkenylation of 1-naphthols was achieved using rhodium(III) catalysis under constant current electrolysis conditions. This strategy offers a wide scope, good functional group tolerance, and high site- and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, Organic
Gopal Krushna Das Adhikari, Smruti Ranjan Mohanty, Shyam Kumar Banjare, Namrata Prusty, Gajiram Murmu, Ponneri C. Ravikumar
Summary: In this study, a method for synthesizing beta-carboline-1-one derivatives from indole-2-carboxamides and bicycloalkenes under mild conditions is reported. The commercially available ruthenium catalyst was used for the reaction. The reaction showed good tolerance towards various functional groups and resulted in high yields of the desired products. Mechanistic studies revealed the involvement of a reversible cyclometalation pathway.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Charles B. Musgrave, Weihao Zhu, Nathan Coutard, Jeffrey F. Ellena, Diane A. Dickie, T. Brent Gunnoe, William A. Goddard
Summary: In this study, we investigated the mechanism of oxidative conversion of benzene and ethylene to styrene using Cu(II) and Rh-Cu-Rh active catalyst. The incorporation of Cu(II) into the active Rh-Cu-Rh catalyst reduced the activation barrier for benzene C-H activation, O-H reductive elimination, and ethylene insertion into the Rh-Ph bond.
Article
Chemistry, Multidisciplinary
Peng Yang, Qiang Wang, Bing-Hui Cui, Xiao-Dong Zhang, Hang Liu, Yue-Yuan Zhang, Jia-Liang Liu, Wen-Yu Huang, Ren-Xiao Liang, Yi-Xia Jia
Summary: This study developed a cobalt-catalyzed enantioselective [3 + 2] annulation of N-heteroarenes with alkynes, providing a straightforward access to a variety of N-spiroheterocyclic molecules with excellent enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Chandan Kumar Giri, Sudeshna Mondal, Mahiuddin Baidya
Summary: A weakly coordinated Ru(II)-catalyzed oxidative functionalization method was developed for the synthesis of ortho-alkenylated benzamides, acetophenones, and benzophenones from unactivated olefins and arenes. The reaction could accommodate various bioactive molecules and enable downstream synthetic manipulations to afford a 2,3-benzodiazepine scaffold. The reaction proceeds via a reversible metalation step and regioselective beta-hydride elimination event.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Shuo-Qing Zhang, Li-Cheng Xu, Shu-Wen Li, Joao C. A. Oliveira, Xin Li, Lutz Ackermann, Xin Hong
Summary: In recent years, there has been a significant increase in the application of machine learning in the field of chemistry, showcasing the potential of data-driven prediction of synthesis performance. This minireview summarizes the latest techniques and designs in synthetic performance prediction, emphasizing the importance of incorporating chemical knowledge in machine learning. It hopes to inspire chemists to revisit the digitalization and computerization of organic chemistry principles.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nikolaos Kaplaneris, Alejandro Puet, Felix Kallert, Julia Poehlmann, Lutz Ackermann
Summary: We achieved the late-stage diversification of structurally complex peptides through palladium-catalyzed C-H arylation. The tunability and ease of preparation of arylthianthrenium salts allowed us to forge sterically congested biaryl linkages between tryptophan-containing peptides and drug, natural product, and peptidic scaffolds. The robustness of the palladium catalysis regime was demonstrated by the full tolerance of sensitive and coordinating functional groups. As a result, we efficiently accessed highly decorated, labelled, conjugated, and ligated linear and cyclic peptides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Silvia Cattani, Andrea Secchi, Lutz Ackermann, Gianpiero Cera
Summary: Iron-catalysed C-H alkylations with alkenes on benzamides were achieved using N-triazole assistance. The regioselectivity can switch from linear to branched depending on the nature of the olefin. This approach allows for the synthesis of a variety of decorated benzamides with high levels of chemo-, regio-, and site-selectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Tristan von Muenchow, Suman Dana, Yang Xu, Binbin Yuan, Lutz Ackermann
Summary: Enantioselective oxidation reactions typically rely on costly transition metals and stoichiometric amounts of chemical oxidants. This study demonstrates a sustainable alternative by using electrocatalysis, specifically the hydrogen evolution reaction (HER), in place of a chemical oxidant. The use of cobalt catalyst for asymmetric oxidation enables highly enantioselective aryl carbon-hydrogen bond (C-H) activation reactions, leading to the synthesis of chiral compounds. Additionally, cobalt-mediated electrocatalysis allows for selective desymmetrization through dehydrogenative C-H activation reactions, facilitating the preparation of sterically complex phosphorus (P)-stereogenic compounds.
Editorial Material
Chemistry, Multidisciplinary
Max Surke, Rong Zhao, Lutz Ackermann
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Binbin Yuan, Joao C. A. Oliveira, Lutz Ackermann
Summary: Transition-metal-catalyzed C-H activation has been widely used as a resource-efficient strategy for molecular synthesis. Weak secondary dispersion interactions play a crucial role in these transformations, affecting kinetic efficacy and selectivity. This Account summarizes our group's recent progress in understanding and quantifying London dispersion effects in transition-metal-catalyzed C-H activation.
Review
Chemistry, Multidisciplinary
Yulei Wang, Suman Dana, Hao Long, Yang Xu, Yanjun Li, Nikolaos Kaplaneris, Lutz Ackermann
Summary: Late-stage functionalization (LSF) is a powerful strategy to accelerate the development of medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical late-stage functionalization (eLSF) has emerged as an environmentally friendly platform and has gained significant momentum in the past decade.
Editorial Material
Chemistry, Organic
Margaret A. Brimble, Lutz Ackermann, Yan-Mei Li, Monika Raj
Article
Chemistry, Physical
Ye Lin, Tristan von Muenchow, Lutz Ackermann
Summary: 3D metallaelectro-catalyzed C-H activation is a promising strategy to obtain valuable organic molecules in an economically and environmentally friendly manner. However, achieving enantioselective C-H activation using 3D metals is challenging and has limited progress. In this study, we combined cobaltaelectro-catalyzed C-H activation with asymmetric catalysis to achieve highly enantioselective annulation of allenes, resulting in a wide range of chiral compounds with good yields and high enantioselectivities. This approach demonstrated practicality by diversifying complex bioactive compounds and drug molecules, as well as conducting large-scale enantioselective electrocatalysis in continuous flow.
Article
Chemistry, Multidisciplinary
Tsuyoshi Oyama, Lorena Mendive-Tapia, Verity Cowell, Adelina Kopp, Marc Vendrell, Lutz Ackermann
Summary: Fluorescent labeling of peptides catalyzed by non-toxic manganese(i) via C(sp(2))-H alkenylation enables the selective and site-specific labeling of peptides, providing access to novel near-infrared nitrobenzodiazole-based peptide fluorogenic probes.
Article
Chemistry, Multidisciplinary
Yan Zhang, Zhenzhi Cai, Chunhang Zhao, Hanliang Zheng, Lutz Ackermann
Summary: Electrooxidative radical cascade cyclization of 1,6-enynes enables the synthesis of sulfonamides with medium-sized rings. The activation barrier difference between alkynyl and alkenyl moieties allows for chemo-selective addition and regioselective ring formation. This metal-free and chemical oxidant-free reaction provides efficient access to sulfonamides with bridged or fused ring systems.
Article
Chemistry, Multidisciplinary
Jian-Biao Liu, Xiao-Jun Liu, Joao C. A. Oliveira, De-Zhan Chen, Lutz Ackermann
Summary: In this study, a radical-type migratory insertion involving synchronous but asynchronous metal-carbon (M-C) bond homolysis and radical attack was discovered through computations. Inspired by this radical migratory insertion, a distinct cobalt-catalyzed radical-mediated carbon-carbon (C-C) cleavage mechanism was proposed for alkylidenecyclopropanes (ACPs). This unique C-C activation mechanism plays a key role in explaining the experimentally observed selectivity for the coupling between benzamides and ACPs. Additionally, the C(sp(2))-H activation in the coupling reaction occurs via the proton-coupled electron transfer (PCET) mechanism instead of the originally proposed concerted metalation-deprotonation (CMD) pathway. The ring opening strategy may lead to further development and discovery of novel radical transformations.
Review
Chemistry, Physical
Julia Struwe, Lutz Ackermann, Fabrice Gallou
Summary: The cross-coupling of terminal acetylenes is frequently required in pharmaceutical and natural product synthesis. Traditional methods using organic solvents have significant environmental and human health impacts. Safer and more sustainable approaches using water as a reaction medium have been developed.
Review
Chemistry, Multidisciplinary
Renato L. de Carvalho, Emilay B. T. Diogo, Simon L. Homoelle, Suman Dana, Eufranio N. da Silva Junior, Lutz Ackermann
Summary: Transition-metal catalyzed C-H activation reactions are effective methods for synthesizing important molecules. Understanding the role of silver salts as additives can help overcome the challenges associated with their use and shift towards silver-free systems.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Chemistry, Organic
Zhenzhi Cai, Sven Trienes, Kairui Liu, Lutz Ackermann, Yan Zhang
Summary: During the past decade, photo- and electrochemical reactions via single-electron-transfer (SET) triggered radical pathways have been widely used to efficiently form chemical bonds. In particular, radical cyclization reactions of 1,n-enynes have been explored for the synthesis of bioactive compounds. This minireview summarizes recent progress in radical cascade cyclizations of 1,n-enynes (n = 5, 6, and 7) under photo/electrochemical conditions until September 2023, providing a categorized overview and understanding for readers.
ORGANIC CHEMISTRY FRONTIERS
(2023)
