Article
Chemistry, Physical
Jose B. Roque, Tyler P. Pabst, Paul J. Chirik
Summary: The use of bis(silylene)pyridine cobalt(III) dihydride boryl as a precatalyst enables efficient hydrogen isotope exchange reactions, including deuterium incorporation at sterically hindered sites and high chemoselectivity towards aryl halides.
Article
Chemistry, Multidisciplinary
Francesco Ferlin, Ioannis Anastasiou, Nihad Salameh, Takeru Miyakoshi, Olivier Baudoin, Luigi Vaccaro
Summary: A heterogeneous catalyst has been prepared for the intramolecular activation/cyclization reaction to synthesize indolines. The catalyst showed high efficiency through a release and catch mechanism, facilitated by iodide ligands. The heterogeneous nature of the catalyst was further utilized in the design of a continuous-flow protocol, enabling efficient recovery and reuse.
Article
Chemistry, Multidisciplinary
Isaac Choi, Antonis M. Messinis, Xiaoyan Hou, Lutz Ackermann
Summary: The research reveals osmaelectrocatalyzed C-H activations using benzoic acids, enabling electrooxidative alkyne annulations with high levels of selectivity. Unprecedented osmium(0) and osmium(II) intermediates were isolated, and detailed mechanistic studies unveiled a facile C-H cleavage and ample substrate scope for annulated heterocycles synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Jiang-Fei Li, Yu-Xin Luan, Mengchun Ye
Summary: Anchoring catalysis involves a reversible interaction between substrates and catalysts to activate inert chemical bonds without the need for preinstalled directing groups. Coordinative bimetallic anchoring catalysis, in particular, displays superior reactivity due to strong interaction and good compatibility with substrates and reaction conditions. Major progress has been made in recent years in the development of coordinative bimetallic anchoring catalysis.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xuefeng Tan, Xiaoyan Hou, Torben Rogge, Lutz Ackermann
Summary: This study achieved the electrochemical three-component assembly of isoquinolines using ruthenium electro-catalyzed C-H/N-H functionalization, demonstrating a robust electrocatalysis with ample substrate scope, efficient electrooxidation, and an operationally friendly procedure. Furthermore, detailed mechanistic studies and unprecedented cyclovoltammetric analysis of a seven-membered ruthenacycle supported an unusual ruthenium(II/III/I) regime.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Nian Li, Jinhang Li, Mingzhe Qin, Jiajun Li, Jie Han, Chengjian Zhu, Weipeng Li, Jin Xie
Summary: This article reports a practical, highly selective and cost-effective hydrogen/deuterium exchange method for unactivated C(sp(3))-H bonds, using photocatalysis and hydrogen atom transfer catalysis. The reaction, using easily prepared PMP-substituted amides as nitrogen-centered radical precursors, leads to selective deuterium incorporation in a wide range of structurally diverse amides, achieving high yields and excellent selectivity.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Nelson Y. S. Lam, Kevin Wu, Jin-Quan Yu
Summary: The design of synthetic routes by retrosynthetic logic is influenced by available transformations. Transition-metal-catalyzed C-H activation is a powerful strategy for C-C bond formation, but its uptake in total synthesis has been tepid due to synthetic intractability and a lack of comprehensive guidelines. This Review addresses these issues and offers a guide to identify retrosynthetic opportunities to generate C-C bonds by C-H activation processes. Comparing traditional approaches and recent C-H activation methods, this Review demonstrates more efficient retrosynthetic strategies enabled by C-H activation for C-C bond construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Pidiyara Karishma, Alisha Gogia, Sanjay K. Mandal, Rajeev Sakhuja
Summary: This study successfully achieved a direct carbocyclization of 2-aryl-2,3-dihydrophthalazine-1,4-diones using isocyanates as the carbonyl source via Ru(II)-catalyzed sequential ortho-amidation followed by intramolecular nucleophilic substitution, delivering substituted indazolo[1,2-b]phthalazine-triones in good-to-excellent yields. Additionally, excellent yields of the corresponding amidated products were obtained for ortho-substituted 2-aryl-2,3-dihydrophthalazine-1,4-diones by modifying the reaction parameters. The use of isocyanates as the carbonyl source, high functional group tolerance on the two coupling partners, and diverse chemical transformation of the synthesized fused and functionalized phthalazinones are the key highlights of this work.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Qiuzhu Wang, Wenjuan Xiao, Honghui He, Jie Guo, Mengning Wang, Mengtao Ma, Binlin Zhao
Summary: A heterogeneous redox-neutral palladium-catalytic platform was developed for the synthesis of deuterated (hetero)arenes from (hetero)arenes via regioselective C(sp(2))-H thianthrenation using a commercially available and recyclable Pd/C catalyst. A wide range of deuterated compounds with high yields and excellent levels of deuterium incorporation could be obtained under these simple heterogeneous catalytic conditions, utilizing stable and easily handled DCOONa as a deuterium source. The late-stage deuteration of pharmaceuticals and bioactive molecules was also successfully achieved.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Zhe An, Hongbo Han, Jianning Zhong, Jian Zhang, Yanru Zhu, Xin Shu, Hongyan Song, Wenlong Wang, Lirong Zheng, Ming Qing, Jing He
Summary: This study presents an elegant strategy for one-pot asymmetric 0-C-H functionalization of aldehydes under O2 catalyzed by hydroxide-layered Fe(III) sites synergistic with confined interlayer amine. The strategy achieves high regioselectivity, stereoselectivity, and yield, providing valuable insights for further research in the field of organic synthesis.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Nahiane Pipaon Fernandez, Gregory Gaube, Kyla J. Woelk, Mathias Burns, Damian P. Hruszkewycz, David C. Leitch
Summary: We present a new method for direct C-C bond formation using tandem C-O/C-H activation mediated by palladium catalyst. This approach allows for base-free direct C-H alkenylation by combining C-O oxidative addition at enol pivalates and concerted metalation-deprotonation of functionalized heterocycles. Mechanistic studies show that C-O oxidative addition is reversible and C-H activation occurs directly from the Pd(II) C-O oxidative addition product. In situ P-31 NMR spectroscopy reveals that (Cy3P)(2)Pd-(alkenyl)(OPiv) species is the predominant catalyst resting state during the reactions.
Article
Chemistry, Organic
Jan Ulc, Jaroslav Jacko, Ivana Cisarova, Lubomir Pospisil, David Necas, Martin Kotora
Summary: Here, the design and synthesis of a series of novel cationic nitrogen-embedded polyaromatic hydrocarbons with a planar geometry are reported. The synthesis pathway is based on catalytic C-C/C-H bond activation relay, enabling the preparation of selectively-regioselective 5,6,10,11-tetrasubstituted naphtho[2,1,8-ija]quinolizinium salts with various substituents. Single-crystal X-ray analysis confirmed the planarity of the quinolizinium core. Most of the synthesized compounds exhibited strong fluorescence, ranging from 420-600 nm, depending on the substitution pattern. DFT calculations revealed that the LUMO is always distributed over the quinolizinium framework while the delocalization of HOMO is related to the substitution pattern. Electrochemical measurements showed irreversible reduction of all compounds, which is consistent with the calculated location of LUMO orbitals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Carla Marie Stork, Remo Weck, Megane Valero, Henrik Kramp, Stefan Guessregen, Siegfried R. Waldvogel, Anna Sib, Volker Derdau
Summary: We have explored the application of highly selective homogeneous iridium-catalyzed hydrogen isotope exchange (HIE) using deuterium or tritium gas as an isotope source in aqueous media. By employing an improved water-soluble Kerr-type catalyst and conducting DFT calculations, we gained insights into the reactivity, transition states, and coordination complexes, guiding the scope and limitations of HIE reactions in water. Additionally, we successfully extended these findings to tritium chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Amarajothi Dhakshinamoorthy, Cristina Valles Garcia, Patricia Concepcion, Hermenegildo Garcia
Summary: In this study, Cu-3(BTC)(BTC: 1,3,5-benzenetricarboxylate) MOF is reported to be an effective catalyst for promoting the borylation of arenes through C-H activation. Compared to other MOFs, Cu-3(BTC) shows higher catalytic activity, with copper ions playing a crucial role in the catalytic mechanism.
Review
Radiology, Nuclear Medicine & Medical Imaging
A. Alsafi, C. L. Shovlin, J. E. Jackson
Summary: This study describes the causes and appearances of transpleural systemic artery-to-pulmonary artery shunts in patients without chronic inflammatory lung disease, and concludes that such shunts are usually related to previous thoracic trauma/intervention or abdominal or pulmonary sepsis involving a pleural or diaphragmatic surface. Congenital shunts are rare, and conservative management is recommended.
CLINICAL RADIOLOGY
(2021)
Article
Chemistry, Physical
Shuai Li, Bethany Jochim, James E. Jackson, Marcos Dantus
Summary: The study utilized ultrafast tunnel ionization to conduct femtosecond time-resolved dynamic measurements on the retro-Diels-Alder reactions of positively charged cyclohexene, norbornene, and dicyclopentadiene, revealing that these reactions take place on a single picosecond timescale on the ionic potential energy surfaces and exhibit vibrational coherence in some cases.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Multidisciplinary Sciences
Yuting Zhou, Grace E. Klinger, Eric L. Hegg, Christopher M. Saffron, James E. Jackson
Summary: This study presents a mild aqueous process using skeletal Ni cathodes for the electrocatalytic hydrogenolysis of diaryl ethers, which enables direct C-O cleavage without initial benzene ring saturation. The authors identified two distinct cleavage mechanisms and discovered the ability of acetone to control the product ring saturation. This research not only addresses the current bottleneck in biomass conversion, but also provides insights into defluorination reactions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Michael J. Cordon, Junyan Zhang, Nohor Samad, James W. Harris, Kinga A. Unocic, Meijun Li, Dongxia Liu, Zhenglong Li
Summary: Cu-La/Beta catalyst shows high selectivity and efficiency in ethanol conversion to C4+olefins, favoring C5+olefin formation, while monometallic Cu/Beta or La/Beta samples are unable to efficiently catalyze the desired product formation.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Zhen Fang, James E. Jackson, Eric L. Hegg
Summary: Electroreduction holds promise as a candidate strategy for depolymerizing lignin, offering a mild, environmentally friendly, and low-cost method to break the most common beta-O-4 bond. This study investigates the room-temperature electroreductive cleavage of four common lignin samples and achieves encouraging results.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Mingxia Zhou, Aimee Lu Church, Michael J. Cordon, Chenyang Li, Rodney D. Hunt, Jae-Soon Choi, Lei Bai, Zhenglong Li, James E. Parks, Michael Z. Hu, Larry A. Curtiss, Rajeev S. Assary
Summary: This study investigates the application of Ca-doped CeO2-based catalysts in the ketonization reaction of acetic acid using a combined experimental and computational approach. Results show that Ca addition decreases the reactivity of acetic acid but stabilizes the catalyst at high temperatures. Computational predictions of the optimal Ca-doped structure provide guidance for future catalyst design and development.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Fan Lin, Mengze Xu, Karthikeyan K. Ramasamy, Zhenglong Li, Jordan Lee Klinger, Joshua A. Schaidle, Huamin Wang
Summary: The article discusses the challenges faced by biomass conversion technologies, specifically in terms of catalyst deactivation and mitigation. It highlights the unique properties of biomass-derived feedstocks that cause catalyst deactivation and provides information on potential mitigation approaches to guide the design of robust catalysts and processes for biomass conversion.
Article
Chemistry, Physical
Sabyasachi Das, James E. E. Anderson, Robert De Kleine, Timothy J. J. Wallington, James E. E. Jackson, Christopher M. M. Saffron
Summary: Quantification of environmental impacts through life cycle assessment is essential for evaluating the potential of bioenergy systems as replacements for fossil-based energy systems. A comparative life cycle assessment was performed to evaluate the performance of a bioenergy system employing Py-ECH versus traditional cellulosic fermentation in three environmental impact categories. The results showed that Py-ECH had lower eutrophication potential and water scarcity footprint compared to cellulosic ethanol production. Increased renewable electricity led to lower greenhouse gas emissions for Py-ECH processing.
SUSTAINABLE ENERGY & FUELS
(2023)
Article
Chemistry, Organic
Sarah E. Luderer, Behrad Masoudi, Aritra Sarkar, Calvin Grant, Arvind Jaganathan, James E. Jackson, Babak Borhan
Summary: Various structural elements of Cinchona alkaloid dimers were studied to establish a structure-enantioselectivity relationship (SER) in three different halocyclization reactions. The sensitivity of SER to linker rigidity and polarity, alkaloid structure, and the presence of alkaloid side groups defining the catalyst pocket varied in the chlorocyclizations. DFT calculations on methoxylated models revealed high barriers to ether rotation, indicating the importance of conformational rigidity in linker-ether connections.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Nanoscience & Nanotechnology
Junjie Chen, Hien N. Pham, Tala Mon, Todd J. Toops, Abhaya K. Datye, Zhenglong Li, Eleni A. Kyriakidou
Summary: Catalytic oxidation of CH4 over nonprecious Ni/CeO2 catalysts with different CeO2 support morphologies (nanoparticles (P), rods (R), cubes (C)) and synthetic procedures (precipitation, sol-gel (SG)) was studied. The relationship among CeO2 morphologies, redox properties, surface areas, and CH4 oxidation activity was established. CeO2-R support showed higher oxygen vacancies, improved OSC and CH4 oxidation activity compared to CeO2-P and CeO2-C supports. The same activity pattern was observed for Ni containing catalysts (Ni/CeO2-R > Ni/CeO2-P > Ni/CeO2-C). Increasing CeO2 surface area by sol-gel synthesis method (CeO2-SG) improved the CH4 oxidation performance of CeO2-SG and Ni/CeO2-SG compared to CeO2-R and Ni/CeO2-R, respectively. All studied Ni/CeO2 nanocatalysts showed improved hydrothermal stability compared to conventional Pd/Al2O3.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Physical
Sabyasachi Das, James E. Anderson, Robert De Kleine, Timothy J. Wallington, James E. Jackson, Christopher M. Saffron
Summary: This study presents a technoeconomic model for decentralized, depot-based pyrolysis with electrocatalytic hydrogenation and centralized upgrading of biomass into liquid hydrocarbon fuel. The results show that this technology is economically feasible and can achieve low-cost production of liquid hydrocarbon fuel.
SUSTAINABLE ENERGY & FUELS
(2022)
Article
Chemistry, Multidisciplinary
Junyan Zhang, Eunji Yoo, Brian H. Davison, Dongxia Liu, Joshua A. Schaidle, Ling Tao, Zhenglong Li
Summary: Ethanol to middle distillates is a promising pathway for sustainable liquid fuel production, leveraging abundant biomass and CO2 utilization, with potential for reducing greenhouse gas emissions. Leveraging existing ethanol infrastructure and catalysis innovation can drive cost-effective production of middle distillate fuels.
Review
Chemistry, Multidisciplinary
Mahlet Garedew, Chun Ho Lam, Laurene Petitjean, Shuquan Huang, Bing Song, Fang Lin, James E. Jackson, Christopher M. Saffron, Paul T. Anastas
Summary: A sustainable bio-based future requires utilizing all components of biomass, including lignin, for various conversion and upgrading schemes to enable economically and environmentally sustainable biorefineries. Electrocatalytic upgrading of lignin-derived intermediates offers a sustainable way to integrate renewable energy sources with biomass conversion, capturing excess renewable electricity in the form of chemical bonds. This technology allows for fine-tuning of selectivity, reduces energy inputs, and presents both challenges and opportunities for future implementation.
Article
Chemistry, Applied
Xianyang Wu, Yaocai Bai, Zhenglong Li, Jue Liu, Kejie Zhao, Zhijia Du
Summary: This study thoroughly investigates the aging mechanism of lithium-ion batteries caused by fast charging using various characterization techniques, revealing that the rapid capacity fading at 6C charging rate is mainly due to Li inventory loss from cathode structure and metallic Li plating on graphite electrode, while changes in electrolyte also affect battery performance.
JOURNAL OF ENERGY CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Debarshi Chakraborty, Hadi Gholami, Aritra Sarkar, Leo A. Joyce, James E. Jackson, Babak Borhan
Summary: A simple chiroptical solution for the absolute stereochemical determination of asymmetric phosphorus V stereocenters is presented in this study. The strong coordination between the phosphorus oxide and the racemic host Zn-MAPOL 2 induces axial chirality of the host, resulting in a strong ECCD signal. A mnemonic is proposed to correlate the asymmetry of the guest molecule with the observed ECCD signal.
