Article
Chemistry, Inorganic & Nuclear
Xiaofan Jia, Songyuan Tian, Philip J. Shivokevich, W. Dean Harman, Diane A. Dickie, T. Brent Gunnoe
Summary: This study reports a new class of Ruthenium(II) complexes that can catalyze the conversion of benzene and ethylene via arene C-H activation. The catalytic performance of these Ru(II) complexes is found to be related to the reduction in electron-density at the Ru center. Three new structurally related Ru(II) complexes are synthesized, characterized, and studied for possible catalytic benzene ethylation.
Article
Chemistry, Multidisciplinary
Takahiro Nishimura
Summary: Hydroarylation reactions using C-H activation to synthesize substituted arenes can compensate for drawbacks of classical methods like Friedel-Crafts reactions. This method involves iridium-catalyzed intermolecular and intramolecular hydroarylation reactions, including asymmetric addition reactions, depending on substrates. It utilizes a cationic iridium catalyst and various ligands to control reactivity and selectivity, along with a described H/D exchange reaction for alkenes.
Article
Chemistry, Physical
Pablo Vazquez-Dominguez, Antonio Romero-Arenas, Rosario Fernandez, Jose Maria Lassaletta, Abel Ros
Summary: The catalytic hydroarylation of alkynes is a useful method for synthesizing functionalized alkenes with excellent control of regio- and stereochemistry. However, there is a scarcity of asymmetric methodologies in this field. In this study, an atroposelective Ir-catalyzed C-H hydroarylation of alkynes was developed, enabling the asymmetric synthesis of axially chiral heterobiaryl trisubstituted olefins with high yields and enantioselectivities up to 98% ee.
Article
Chemistry, Inorganic & Nuclear
Sangeeta Kumari, Charu Sharma, Avinash K. Srivastava, Naveen Satrawala, Kamal N. Sharma, Raj K. Joshi
Summary: A Ru(II) complex was synthesized for C-H bond activation alkenylation of arenes using thioether directing groups, achieving high yields under milder conditions compared to previous methods utilizing precious noble metal catalysts. Broad substrate scope was demonstrated with good tolerance towards benzyl thioethers and vinyl, making it the first report of its kind utilizing a Ru-based catalyst for thioether alkenylation.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Roushan Prakash Singh, Soumen Sinhababu, Neal P. Mankad
Summary: This Perspective reviews recent advances and applications of Al/M heterobimetallic catalysis in various areas, including polymerization, epoxide activation and carbonylation. The mechanistic role of the aluminum site is highlighted, and a comprehensive perspective is constructed by including a broad range of Al-containing metalloligands and Al/M combinations.
Article
Chemistry, Applied
Liangliang Song, Gerardo M. Ojeda-Carralero, Divyaakshar Parmar, David A. Gonzalez-Martinez, Luc Van Meervelt, Johan Van Der Eycken, Jan Goeman, Daniel G. Rivera, Erik V. Van der Eycken
Summary: This report presents a ruthenium-catalyzed C-H activation/annulation process that can selectively modify the peptide backbone to produce functionalized isoquinolone scaffolds with high regioselectivity in a rapid and step-economical manner. The method allows for the production of fluorescent peptides, peptide conjugates with drugs, natural products, and other peptide fragments, providing a chemical approach for constructing novel peptide-pharmacophore conjugates.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Martin Vuagnat, Vincent Tognetti, Philippe Jubault, Tatiana Besset
Summary: A practical and straightforward synthesis of beta-(E)-trifluoromethylstyrenes by ruthenium-catalyzed C-H bond activation has been developed. The use of 2-bromo-3,3,3-trifluoropropene as a reservoir of 3,3,3-trifluoropropyne enables the safe and scalable monofunctionalization of a variety of heteroarenes. Mechanistic investigations and DFT calculations provide insights into the mechanism of this transformation, highlighting the role of a cyclometallated ruthenium complex.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yaohang Cheng, Yuhang He, Jie Zheng, Hui Yang, Jun Liu, Guanghui An, Guangming Li
Summary: The method developed utilizes Ru(II) catalysis to facilitate the synthesis of challenging difluoroalkylated aldehydes and ketones with para-selectivity.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Timothy P. Aldhous, Raymond W. M. Chung, Andrew G. Dalling, John F. Bower
Summary: This review presents recent intermolecular enantioselective Murai-type alkene hydroarylation methodologies and the mechanisms by which they proceed, providing an efficient way to achieve enantioselective hydroarylations of alkenes with benzylic stereocenters.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Marie Peng, Denis Ari, Thierry Roisnel, Henri Doucet, Jean-Francois Soule
Summary: We present a versatile Rh(i)-catalyzed cascade reaction that combines C(sp(2))-H bond functionalization and amidation between N-arylphosphanamines and acrylates. This innovative approach allows for the rapid synthesis of dihydroquinolinone scaffolds, which are commonly found in various pharmaceuticals. The involvement of a Rh-H intermediate and the substrate inhibition through catalyst saturation were revealed through detailed mechanistic investigations.
Article
Chemistry, Multidisciplinary
Nurbey Gulia, Jaroslaw Fornalski, Adrianna Gumienna, Malgorzata Ambroziak, Slawomir Szafert
Summary: This study reports a method of palladium-catalyzed C-H arylation assisted with a 3,4,4-trimethylpyrazol-5-on directing group, which selectively provides mono- and di-ortho-arylated products. The steric hindrance between the directing group and the already introduced aryl substituent enables control of mono- vs. diarylation selectivity by the reaction temperature. A series of monosubstituted and disubstituted derivatives were obtained in good yields. In addition, a one-pot procedure for unsymmetrical double-arylation to give corresponding products was developed, and the synthesis and X-ray study of intermediate palladium metallacycles were conducted. The decarboxylative cleavage of the pyrazolone directing group under mild conditions gave synthetically useful hydrazones. Overall, this solution provides an alternative synthetic pathway for ortho arylated derivatives of arylhydrazines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jun Wu, Nikolaos Kaplaneris, Julia Poehlmann, Takuya Michiyuki, Binbin Yuan, Lutz Ackermann
Summary: The prevalence of C-aryl glycosides in biologically active natural products and approved drugs has motivated the development of efficient synthesis strategies. Palladium catalysts with prefunctionalized substrates have been commonly used, while ruthenium-catalyzed C-aryl glycoside synthesis has been challenging. In this study, a versatile ruthenium(II)-catalyzed meta-C-H glycosylation method was disclosed, allowing for the synthesis of meta-C-aryl glycosides from readily available glycosyl halide donors. The ruthenium catalysis exhibited mild reaction conditions, exceptional levels of anomeric selectivity, and exclusive meta-site-selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Binyang Jiang, Jia-Ming Liu, Shi-Liang Shi
Summary: Achieving site-selective C2-alkylation of pyridine using unactivated alkene as an alkylating reagent is a long-standing challenge. In this study, a bifunctional NHC-Ni-Al-pyridine complex under Ni-Al bimetallic catalysis and directing bifunctional N-heterocyclic carbene (NHC) as ligand was used to achieve high site selectivity and efficiency in the C2-alkylation of pyridine.
Article
Chemistry, Physical
Binyang Jiang, Jia-Ming Liu, Shi-Liang Shi
Summary: We report a method for achieving site-selective C2-alkylation of pyridine using unactivated alkenes as alkylating reagents under Ni-Al bimetallic catalysis and directing bifunctional N-heterocyclic carbene (NHC) as a ligand. The method allows for the efficient synthesis of a wide range of C2-alkylated pyridines with various functionalities, and can be extended to other azines such as pyrazines and pyrimidines. Mechanistic studies reveal that a bifunctional NHC-Ni-Al-pyridine complex is responsible for high site selectivity control, and reductive elimination may be the rate-determining step.
Article
Chemistry, Multidisciplinary
Jun Wu, Wen Wei, Julia Poehlmann, Rajeshwaran Purushothaman, Lutz Ackermann
Summary: In this study, a ruthenium(II)-catalyzed multicomponent Domino reaction was reported, which enables the efficient synthesis of structurally diversified C-alkyl glycosides in a single step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, 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)
Review
Chemistry, Multidisciplinary
Yan Zhang, Zhenzhi Cai, Svenja Warratz, Chanchan Ma, Lutz Ackermann
Summary: In recent years, electrochemical oxidative reactions using radical intermediates have become an environmentally friendly and powerful method for the formation of C-E (E = C, N, S, Se, O and Hal) bonds through single-electron transfer processes at the electrodes. This minireview focuses on the recent advances in electrooxidation and radical reactions, particularly concerning radical additions onto alkynes, until June 2022.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xinran Chen, Hasret Can Guelen, Jun Wu, Zi-Jing Zhang, Xin Hong, Lutz Ackermann
Summary: Ruthenium-catalyzed sigma-bond activation-assisted meta-C-H functionalization has gained significance in the formation of distal C-C bonds. However, the lack of mechanistic studies has hindered a complete understanding of the site-selectivity and reaction pattern. In this study, computational investigations were conducted on ruthenium-catalyzed C-H functionalization using alkyl bromides and aryl bromides. Monocyclometalated ruthenium(II) complexes were identified as the active species, with inner-sphere single electron transfer (ISET) facilitating the activation of organic bromides. The competition between reductive elimination and radical coupling determines the site-selectivity, which was further predicted using a multilinear regression model validated by experiments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan Zhang, Chunhang Zhao, Chanchan Ma, Zhenzhi Cai, Lutz Ackermann, Sven Trienes
Summary: We describe a mechanistically distinct approach using photoinduced carbon-carbon (C-C) activation/ring-opening to access gamma,delta-unsaturated aldehydes from methylenecyclobutanols and sulfonyl chlorides by strain release. The sulfonyl motif on the products was easily removed by another photocatalytic process, enabling the concise assembly of the natural product alatanone A. Our approach demonstrates versatile functional group tolerance, ample substrate scope, and scalability, and represents a conceptually distinct alternative to existing approaches for remote 1,4-diversifications, with a double bond remaining in the obtained products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shan Chen, Binbin Yuan, Yulei Wang, Lutz Ackermann
Summary: By difunctionalization of nonactivated alkenes, twofold distal C-H functionalization was achieved, allowing rapid access to multifunctionalized molecules. The multicomponent ruthenium-catalyzed remote 1,n-difunctionalization (n=6,7) of nonactivated alkenes with fluoroalkyl halides and heteroarenes in a modular manner was reported. This method provided mild conditions, unique selectivity, and broad substrate scope, and featured a domino process for twofold remote C(sp(2))-H/C(sp(3))-H activation with the sequential formation of three different carbon-centered radicals. A plausible mechanism was proposed based on detailed experimental and computational studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jun Wu, Wen Wei, Julia Poehlmann, Rajeshwaran Purushothaman, Lutz Ackermann
Summary: In this study, a ruthenium(II)-catalyzed multicomponent Domino reaction was reported, which enables the efficient synthesis of structurally diversified C-alkyl glycosides in a single step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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.
Article
Chemistry, Multidisciplinary
Kui Zeng, Ruhuai Mei, Sebastian Dechert, Lutz Ackermann, Kai Zhang
Summary: This study reports a recyclable stereoauxiliary aminocatalytic approach for the efficient one-pot synthesis of desired trisubstituted indolizine-2-carbaldehydes via [3+2] annulations of acyl pyridines and alpha,beta-unsaturated aldehydes, using aminosugars derived from biomass. Control experiments confirm the stereoauxiliary effect favored by the beta-anomer of D-glucosamine. Moreover, polymeric chitosan containing predominantly beta-D-anhydroglucosamine units shows excellent catalytic performance and can be used for large-scale synthesis and catalytic cycling experiments. Thus, this approach advances the existing methodologies and provides a rich library of indolizine-2-aldehydes, which can be used for late-stage diversification and targeted modifications of bioactive molecules or drugs.
COMMUNICATIONS CHEMISTRY
(2023)
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.
Article
Chemistry, Multidisciplinary
Elisa Y. Lai, Binbin Yuan, Lutz Ackermann, Magnus J. Johansson
Summary: In this study, a new method for directed ruthenium-catalyzed C-H aminocarbonylation has been developed under mild conditions through high-throughput experimentation. This method allows the introduction of special amide functional groups and is applicable to various substitution patterns and different weakly Lewis basic directing groups in anilides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
Meteorology & Atmospheric Sciences
S. P. Alexander, A. Protat, A. Berne, L. Ackermann
Summary: Antarctic precipitation, especially within the boundary layer, is poorly characterized and understood due to limited surface-based remote sensing observations. This study used cloud and precipitation remote-sensing instruments to characterize snowfall over Davis. The results reveal the relationship between virga and wind conditions, particle aggregation at certain temperatures, and the sublimation of snowfall mass at different altitudes. These findings contribute to a better understanding of snowfall in the Antarctic region.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2023)
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)