Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hyotaik Kang, Lida Tan, Jing-Tan Han, Chia-Yu Huang, Hui Su, Aleksei Kavun, Chao-Jun Li
Summary: We demonstrate the use of gallium nitride (GaN) as a non-toxic, recyclable, heterogeneous photocatalyst in conjunction with the catalytic use of benzophenone to activate alkyl C(sp(3))-H bonds and generate alkyl radicals. This dual photocatalytic cycle enables cross-dehydrogenative Minisci alkylation under mild and chemical oxidant-free conditions.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Organic
Aki Takeda, Hayaki Okai, Kyoji Watabe, Hiroki Iida
Summary: In this study, the oxidative cross-dehydrogenative coupling reaction between amidines and chalcones catalyzed by flavin and iodine was demonstrated. The riboflavin-iodine catalytic system played multiple roles in substrate and O-2 activation, enabling the facile and atom-economical synthesis of tetra substituted imidazoles in good yields (60-87%). This metal-free reaction consumed only 1 equiv of molecular oxygen and generated 2 equiv of environmentally benign H2O as the only byproduct.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Vishal Jyoti Roy, Partha Pratim Sen, Sudipta Raha Roy
Summary: A new method for synthesizing thioesters at room temperature through photochemical reaction between aldehyde feedstocks and thiol ethers was introduced. The method has high efficiency and scalability, and can yield desired products under optimized conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Elena R. Lopat'eva, Igor B. Krylov, Oleg O. Segida, Valentina M. Merkulova, Alexey I. Ilovaisky, Alexander O. Terent'ev
Summary: In this study, a hybrid photocatalytic system involving both TiO2 and NHPI was proposed for the cross-dehydrogenative C-C coupling. Each of the catalysts was ineffective when used separately under visible light in this transformation. The high catalytic efficiency was attributed to the interaction of NHPI with the TiO2 surface and the generation of PINO radicals upon visible light irradiation.
Review
Chemistry, Multidisciplinary
Jianbin Li, Chia-Yu Huang, Chao-Jun Li
Summary: This review summarises recently developed strategies for achieving C-C cross-couplings between an inert aliphatic C-H bond and another C-H bond through different C(sp3)-H functionalisation tactics.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Physical
Shuangfei Jiang, Zeqi Jiang, Jin Gao, Wenchao Zhu, Xi Chen, Bo Chen, Qiaoyu Gan, Ling Yuan, Guilan Huang, Han Yu, Lixin Ma, Xinghua Zhang
Summary: In this study, the oxidative dehydrogenation performance of a Lindquist-type polyoxomolybdate was investigated. This inorganic molecular catalyst showed efficient cross-dehydrogenative coupling of P(O)H compounds and thiols under visible light irradiation, without the need for metals, bases, or external oxidants. It demonstrated good stability and reusability, making it a promising alternative photocatalyst for oxidative dehydrogenative processes.
Article
Chemistry, Organic
Xuan Guo, Bing-ru Shao, Wen-feng Jiang, Lei Shi
Summary: A new strategy for cross-dehydrogenative C-C and C-P coupling reaction without the use of a photocatalyst has been developed. This method allows for the synthesis of various 1-substituted tetrahydroisoquinoline derivatives through visible-light direct excitation of substrates. The broad substrate scope demonstrates good synthetic versatility and practicality.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
C. M. A. Afsina, Thaipparambil Aneeja, Mohan Neetha, Gopinathan Anilkumar
Summary: Copper-catalyzed organic reactions have attracted widespread attention due to the abundance and affordability of copper, as well as its low toxicity, eco-friendliness, sustainable nature, and versatility as a catalyst. These reactions are primarily used for the synthesis of biologically important nitrogen heterocycles, amines, amides, imines, and alkynes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Luca Capaldo, Lorenzo L. Quadri, Daniele Merli, Davide Ravelli
Summary: A novel photoelectrochemical strategy was developed for the cross-dehydrogenative coupling of unactivated aliphatic hydrogen donors with benzothiazoles. By using a specific photocatalyst to activate strong C(sp(3))-H bonds in the substrates, while utilizing electrochemistry to scavenge extra electrons, the reaction was efficiently achieved.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Dong-Yang Han, Xiao-Peng Liu, Ruo-Pu Li, Da-Zhen Xu
Summary: A highly efficient strategy has been developed for the direct thiolation of phenols under transition metal-free and solvent-free conditions. The reactions are operationally simple and employ air as an ideal oxidant, providing mono- and dithiolation products in good to excellent yields under basic conditions. This method tolerates a broad range of aryl thiols and arenes, making it especially applicable for large-scale synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Wei Wei, Xiaodan Zhao
Summary: The carbon-carbon bond-forming cross-dehydrogenative coupling reaction using organoselenium catalysis involving a high-valent para-methoxyphenyl selenium species has been developed. This method enables the synthesis of alpha,alpha-disubstituted alpha-amino acid derivatives with excellent regioselectivities through vinyl or allylic C-H functionalization. The generality of this method has been demonstrated by the cross-coupling of an alkene with an oxindole and the direct functionalization of electron-rich arenes with azlactones.
Article
Chemistry, Multidisciplinary
Gyumin Kang, Sunkyu Han
Summary: In this study, we successfully synthesized dimeric high-oxidation-state securinega alkaloid Flueggeacosine B via two synthetic routes. The second-generation synthesis was more streamlined and a new reaction was developed to provide a direct pathway for the synthesis of compounds with a conjugated dicarbonyl moiety.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhijun Li, Xiaowen Lu, Rufang Zhao, Siqi Ji, Mingyang Zhang, J. Hugh Horton, Yang Wang, Qian Xu, Junfa Zhu
Summary: Researchers have developed an efficient molten-salt-assisted approach to create atomically dispersed cobalt atoms supported over vanadium pentoxide layered material. This cobalt single-atom catalyst achieves extraordinary catalytic efficiency in the dehydrogenative coupling reaction of alcohols and amines, with high selectivity and conversion. Density functional theory calculations confirm the optimized coordination environment and strong metal-support interaction contribute significantly to the activation of reactants.
Article
Chemistry, Multidisciplinary
Jun Xu, Lin Huang, Lei He, Chenfeng Liang, Yani Ouyang, Jiabin Shen, Min Jiang, Wanmei Li
Summary: This study introduces a green and efficient metal-free cross-dehydrogenative coupling (CDC) method for the direct para-C-H heteroarylation of anilines with quinoxalinones. The reaction, performed in H2O/DMSO using air as the sole oxidant, shows good compatibility with various anilines and quinoxalinones, yielding moderate-to-good products. This methodology offers an environmentally friendly and efficient alternative for late-stage modification of nitrogen-containing compounds.
Article
Chemistry, Multidisciplinary
Michael Traxler, Susanne Reischauer, Sarah Vogl, Jerome Roeser, Jabor Rabeah, Christopher Penschke, Peter Saalfrank, Bartholomaeus Pieber, Arne Thomas
Summary: The multicomponent approach is used to create bifunctional materials for cooperative catalysis by incorporating multiple functionalities into a single covalent organic framework (COF). These COFs have a well-defined structure for structure-activity relationship studies. Nickel-loaded COFs containing acridine and 2,2'-bipyridine linkers connected through 1,3,5-benzenetrialdehyde derivatives are reported. The acridine motif enables broad light absorption, while the bipyridine unit allows complexation of nickel catalysts, making the framework materials suitable for light-mediated carbon-heteroatom cross-couplings. Switching between high charge-carrier mobility and charge-separated species can be achieved by varying the node units, tailoring the materials for specific reactions. Nickel-loaded COFs are recyclable and can catalyze cross-couplings using red light irradiation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Thea S. Mayer, Tobias Taeufer, Sina Brandt, Jabor Rabeah, Jola Pospech
Summary: In this study, we demonstrate a photomediated hydro- and deuterodecarboxylation of carboxylic acids using an organic pyrimidopteridine photoredox catalyst. The reaction was optimized using a statistical design of experiment and successfully converted NSAID tablets and larger quantities. This method can be applied to primary, secondary, and tertiary aliphatic biologically active carboxylic acids with high deuterium incorporation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Abdallah I. M. Rabee, Dan Zhao, Sebastian Cisneros, Carsten R. Kreyenschulte, Vita Kondratenko, Stephan Bartling, Christoph Kubis, Evgenii Kondratenko, Angelika Brueckner, Jabor Rabeah
Summary: Gold-based catalysts with low gold loading supported on TiO2 and ZrO2 were synthesized and characterized. The Au/TiO2 catalyst showed higher activity than Au/ZrO2 at 250℃, with different reaction mechanisms involved.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Multidisciplinary
Xingchao Dai, Xinzhi Wang, Carsten Kreyenschulte, Hangkong Yuan, Angelika Brueckner, Feng Shi, Jabor Rabeah
Summary: Value-added formamides were synthesized sustainably by catalyzing in situ C-C bond cleavage with zeolite 5A supported Cu-based catalysts using glycerol derivatives as the carbonyl source. The introduction of Zr-IV ions greatly increased the activity of the Cu/5A catalyst. Isotopic tracing experiments confirmed the involvement of glycerol derivatives in the formation of formamide products.
Article
Chemistry, Physical
Qiyang Zhang, Jabor Rabeah, Thanh Huyen Vuong, Tatiana Otroshchenko, Evgenii V. Kondratenko
Summary: The metathesis reaction of ethylene and 2-butene to produce propene is widely used in the chemical industry. MoOx-based supported catalysts show potential as alternatives to the currently employed WOx-containing systems. The activity of these catalysts depends on the formation of active Mo-carbene sites, which can be controlled by promoting the support with small amounts of alkali or alkaline earth metal oxides. The electronegativity of the additives affects olefin adsorption and carbene formation.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Polymer Science
Jinglun Zhou, Linlin Li, Dengxu Wang, Lihong Wang, Yuanqi Zhang, Shengyu Feng
Summary: In this paper, the concept of bioassimilated carbon is proposed to accurately determine polyolefin-based degradable plastics. A method for detecting the carbonyl index and bioassimilated carbon conversion rate in polyolefin degradable plastics is developed to quickly identify its degradation performance. The detection cycle of plastic deterioration can be shortened from 1 year to 1 month, and this method has the potential to be a relevant standard method for accurately assessing plastic degradation.
Article
Nanoscience & Nanotechnology
Bishal Boro, Ratul Paul, Hui Ling Tan, Quang Thang Trinh, Jabor Rabeah, Chia-Che Chang, Chih-Wen Pao, Wen Liu, Nam-Trung Nguyen, Binh Khanh Mai, John Mondal
Summary: In this study, a unique metalated porous organic polymer was synthesized using a cost-effective approach, and it exhibited superior catalytic performance for low-temperature reactions in water. The polymer addressed some drawbacks of conventional catalytic systems.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Ali M. Abdel-Mageed, Bunyarat Rungtaweevoranit, Sarawoot Impeng, Joachim Bansmann, Jabor Rabeah, Shilong Chen, Thomas Haering, Supawadee Namuangrak, Kajornsak Faungnawakij, Angelika Brueckner, R. Juergen Behm
Summary: Elucidating the reaction mechanism of CO oxidation using a molecularly defined copper single-atom catalyst supported by UiO-66 metal-organic framework (Cu/UiO-66) was achieved through a combination of in situ/operando spectroscopies, kinetic measurements, and density-functional-theory-based calculations. The study identified the active site, reaction intermediates, and transition states of the dominant reaction cycle, as well as changes in oxidation/spin state during the reaction. The reaction involves the continuous dissociation of adsorbed O-2, leading to the formation of an O atom connecting the Cu center with a neighboring Zr4+ ion as the rate-limiting step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Jing Tang, Shengyu Feng, Dengxu Wang
Summary: A series of novel sulfur-containing functionalized disiloxanes were prepared by thiol-epoxy click reaction using 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane and various thiol compounds. The reaction conditions were optimized, and both lithium hydroxide and tetrabutylammonium fluoride showed high catalytic activity, resulting in high yields, excellent regioselectivity, mild reaction conditions, and good tolerance of functional groups. These compounds exhibited unique fluorescence properties due to the formation of coordination bonds between Si atoms and heteroatoms (S or N), emitting blue fluorescence under UV irradiation. The thiol-epoxy click reaction is a promising synthetic methodology for constructing various organosilicon materials with novel structures and functionality.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Chenyang Wang, Phong Dam, Mohamed Elghobashy, Angelika Brueckner, Jabor Rabeah, Luis Miguel Azofra, Osama El-Sepelgy
Summary: In this study, a biomimetic method for the catalytic deammoniation of diverse primary amines is presented. This method offers operational simplicity and high selectivity, providing a rapid pathway to olefin products derived from nonfossil-based chemicals. The use of acridinium salt and cobaloxime as readily available photoactive catalysts enables this unconventional dehydroamination process.
Article
Polymer Science
Jinhua Qian, Fuying Dong, Xiaohui Chen, Xianying Xu, Dongkang Zhang, Fulong Li, Yuxia Gao, Huadong Sun, Laixue Pang, Xinde Tang, Dengxu Wang
Summary: In this study, a novel polysiloxane-modified asphalt was developed by mixing polysiloxane into base asphalt, which can improve the performance of asphalt and meet the requirements of modern asphalt pavement. Through a series of experiments and tests, it was demonstrated that polysiloxane-modified asphalt has good compatibility, lower glass transition temperature, and higher rutting parameter, leading to better performance in high/low-temperature environments.
Article
Chemistry, Physical
Shuoping Ding, Jose Balena Gabriel Filho, Tim Peppel, Simon Haida, Jabor Rabeah, Norbert Steinfeldt, Jennifer Strunk
Summary: Two-dimensional ZnIn2S4 nanosheets were synthesized via a trisodium citrate-assisted hydrothermal method and used for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) and 5-formyl-2-furan (FFCA) with atmospheric O-2 under visible light irradiation. The conversion of HMF reached 95%, and the DFF selectivity was 70% after 1.5 h of illumination. Photogenerated holes (h(+)), O-2(-) and carbon-centred radicals are the dominant reaction species.
SUSTAINABLE ENERGY & FUELS
(2023)
Article
Chemistry, Physical
Shuoping Ding, Igor Medic, Norbert Steinfeldt, Tianao Dong, Tim Voelzer, Simon Haida, Jabor Rabeah, Juncheng Hu, Jennifer Strunk
Summary: Constructing hierarchical and ultrathin-structured metal sulfides is beneficial for efficient hydrogen evolution catalysts. In this study, ZnIn2S4 hollow nanoflowers composed of ultrathin nanosheets were creatively synthesized through a trisodium citrate-mediated and stirring-assisted solvothermal method. The optimized ZnIn2S4 hollow nanoflowers exhibited a high photocatalytic hydrogen generation rate and can be obtained without the need for a cocatalyst.
Article
Chemistry, Multidisciplinary
Chenyang Wang, Luis Miguel Azofra, Phong Dam, Edelman J. Espinoza-Suarez, Hieu Trung Do, Jabor Rabeah, Angelika Brueckner, Osama El-Sepelgy
Summary: In this study, an intramolecular endo-selective Heck reaction of iodomethylsilyl ethers of phenols and alkenols was reported. The reaction resulted in the formation of seven- and eight-membered siloxycycles in excellent yields, which could be further converted into the corresponding allylic alcohols upon oxidation. This method could be used for the selective (Z)-hydroxymethylation of o-hydroxystyrenes and alkenols. Rapid scan EPR experiments and DFT calculations suggested a concerted beta-hydrogen elimination event to take place in the triplet state.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Prasenjit Das, Gouri Chakraborty, Jerome Roeser, Sarah Vogl, Jabor Rabeah, Arne Thomas
Summary: Multicomponent reactions (MCRs) are employed to incorporate different functionalities into stable covalent organic frameworks (COFs). In this study, irreversible three-component Doebner reaction is utilized to synthesize chemically stable DMCR-COFs equipped with acid-base bifunctionality. These DMCR-COFs exhibit superior photocatalytic H2O2 evolution compared to Imine-1, showcasing their potential as materials for solar to chemical energy conversion.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
