Article
Chemistry, Physical
Andrey S. Kozlov, Oleg I. Afanasyev, Denis Chusov
Summary: Borrowing hydrogen amination is a common method for the formation of C-N bonds, which can be carried out without transition metal catalysts at low temperatures. Through experimental investigation, optimal conditions can be predicted and the need for transition metal catalysts can be determined.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Applied
Leo Bettoni, Nicolas Joly, Jean-Francois Lohier, Sylvain Gaillard, Albert Poater, Jean-Luc Renaud
Summary: The borrowing hydrogen strategy was used in a tandem three-component reaction catalyzed by a phosphine free diaminocyclopentadienone ruthenium tricarbonyl complex to synthesize nonsymmetric N,N-dialkylated acyl hydrazides. Different aromatic acyl hydrazides underwent dialkylation with various alcohols in mild reaction conditions, with primary or secondary alcohols serving as the hydrogen source. DFT calculations showed that the tandem mixed product formation could be influenced by the physical state of the aldehyde or ketone intermediate.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Rahul Sharma, Avijit Mondal, Arup Samanta, Nandita Biswas, Babulal Das, Dipankar Srimani
Summary: The borrowing hydrogen method is an important synthetic transformation, and designing cheap and stable catalysts is a key challenge. In this study, easily accessible and stable SNS-Ni complexes were successfully synthesized and applied for the C-alkylation reaction of ketone enolates, showing good functional group tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Kun-Long Dai, Qi-Long Chen, Wen-Ping Xie, Ka Lu, Zhi-Bo Yan, Meng Peng, Chang-Kun Li, Yong-Qiang Tu, Tong-Mei Ding
Summary: A facile benzylic alkylation method has been developed using a newly investigated Ir-III catalyst, which provides high regioselectivity and yield of alkylated indenes and arenes from readily available alcohols. This method has potential applications in the synthesis of analogs and functional materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Talla V. R. Mohan, Madhu Nallagangula, Krishnan Kala, Carlos E. Hernandez-Tamargo, Nora H. De Leeuw, Kayambu Namitharan, Venugopal T. Bhat, Manickam Sasidharan, Parasuraman Selvam
Summary: Metal-free carbonaceous materials are being used as heterogeneous catalysts for sustainable chemistry. However, designing catalytic materials with unique properties for specific organic transformations is challenging due to a lack of understanding of their active sites. In this study, nitrogen-doped ordered mesoporous carbons were used as a biomimetic catalyst for borrowing-hydrogen or hydrogen-auto-transfer reactions. The results show that the local nitrogen environment plays a critical role in catalytic hydrogen shuttles, mimicking the role of the NAD(P)+/NAD(P)H redox couple.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Peifeng Su, Zhe Chen, Jinyu Ni, Zhenjie Yang, Yinwu Li, Zhuofeng Ke
Summary: This study demonstrates the importance of overcoming the alkoxide trap problem and the impact of the chromium center's oxidation state on catalytic activity. By surmounting the alkoxide trap, a Cr(0) catalyst is developed for efficient C-alkylation between alcohols via borrowing hydrogen/hydrogen autotransfer. The Cr(0) catalyst shows excellent catalytic performance and can avoid the d-p p interaction, overcoming the thermodynamic sink caused by the alkoxide trap. This strategy could be helpful in developing efficient and nonprecious transition metal catalysts.
Article
Chemistry, Physical
Jonas Elfert, Anup Bhunia, Constantin G. Daniliuc, Armido Studer
Summary: In this study, a radical transformation that enables intramolecular oxygen atom transfer to alkenes using the nitro functionality in nitroarenes as an oxygen donor is disclosed. The reaction proceeds via iron-catalyzed metal hydrogen atom transfer to alkenes and subsequent oxygenation, resulting in alkene hydration. Compared to intermolecular radical oxygenation, the intramolecular variant offers advantages, particularly in terms of diastereoselective radical hydration of conformationally flexible alkenes. The aryl moiety connecting the reactive NO2-functionality to the alkene substrate can be cleaved after oxygen transfer, yielding products derived from a formal diastereoselective intermolecular alkene hydration. Additionally, the resulting aniline entity after oxygen transfer can be used for the construction of nitrogen-containing heterocycles.
Article
Chemistry, Physical
Jiajia Pan, Jiahao Li, Xiao-Feng Xia, Wei Zeng, Dawei Wang
Summary: An unsymmetrical 2-(diphenylphosphino) aminobenzothiazole (DPA) was used to synthesize a heterogeneous and recyclable palladium composite through co-doping C3N4. The resulting palladium composite (DPA-Pd@g-C3N4) was successfully applied to the synthesis of N-substituted aminopyridine derivatives.
Article
Chemistry, Applied
Lan Luo, Hongqiang Liu, Wei Zeng, Wenkang Hu, Dawei Wang
Summary: A novel and efficient ligand and corresponding rhodium composite were successfully synthesized, showing good catalytic activity and recovery performance in the synthesis of quinoxaline. Additionally, the rhodium composite exhibited good catalytic performance in the synthesis of functionalized ketone through borrowing hydrogen strategy.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tao Yan, Ben L. Feringa, Katalin Barta
Summary: The direct N-alkylation of alpha-amino acid esters and amides with alcohols is achieved through a robust and general ruthenium-catalyzed method, allowing for excellent retention of stereochemical integrity. The use of diphenylphosphate as additive is crucial for enhancing reactivity and selectivity, with water being the only by-product and both substrates potentially derived from renewable resources.
Article
Chemistry, Inorganic & Nuclear
Jiajun Wu, Subash Nethaji Narayanasamy, Christophe Darcel
Summary: In this study, an alpha-alkylation reaction involving methyldiarylphosphine oxides and (hetero)arylmethanols as the electrophilic partners was performed using an iron-based catalyst under hydrogen borrowing conditions. Various (hetero)arylmethanols can be used, leading to the formation of alkyldiarylphosphine oxides with moderate to good yields.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Review
Chemistry, Physical
Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This paper summarizes our team's efforts over the past two decades in the development of new catalytic methods for C-C bond formation. The versatile applications of the commercially available catalyst RuHCl(CO)(PPh3)(3) (or RuH for short) are highlighted through eight different transformations. The fundamental steps involved in the catalysis are emphasized, demonstrating how our mechanistic understanding and the diverse catalytic capabilities of RuH can be utilized to design desired catalytic cycles and develop new cross-coupling reactions with high atom-economy.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Kuhali Das, Milan K. Barman, Biplab Maji
Summary: Catalytic hydrogen transfer reactions are essential for the production of diverse molecular scaffolds, with manganese emerging as a viable alternative due to its abundance and sustainability. Strategies such as metal-ligand bifunctionality and hemilability play crucial roles in achieving desired catalytic activity and selectivity. The use of multifunctional ligand-based manganese complexes in various organic transformations has been detailed, highlighting the importance of ligand design for successful HT reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Nitish K. Garg, Mattias Tan, Magnus T. Johnson, Ola F. Wendt
Summary: Borrowing hydrogen reactions are useful for sustainable C-C and C-N bond synthesis. Two catalytic transformations, N-alkylation of amines with alcohols and β-alkylation of secondary alcohols with primary alcohols, can be effectively carried out with catalytic amounts of base under air without using transition metal-based catalysts. The mechanism involves air oxidation of alcohols to aldehydes, followed by condensation to unsaturated intermediates and transfer hydrogenation with alcohols to produce the desired products.
Article
Chemistry, Physical
Guanxin Zhu, Zheng-Chao Duan, Haiyan Zhu, Minghui Qi, Dawei Wang
Summary: A new and efficient BPS ligand was designed, and corresponding iridium and copper catalysts were synthesized and characterized. The iridium composite showed excellent catalytic activity for the reaction of tert-butanesulfinamide with benzyl alcohols, while the copper catalyst was able to synthesize unsaturated carbonyl compounds from benzyl alcohols and ketones efficiently with good recovery performance.
MOLECULAR CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Peter Bellotti, Huan-Ming Huang, Teresa Faber, Frank Glorius
Summary: The emergence of modern photocatalysis has revolutionized late-stage C-H functionalization, offering unprecedented regio- and chemoselectivities. This Review focuses on the strategies of small-molecule drugs, agrochemicals, and natural products, highlighting the main mechanistic scenarios and comparing established ionic chemistry and photocatalyzed radical-based manifolds. The authors aim to provide a comprehensive overview of the current state-of-the-art and address the challenges and future directions in this field.
Article
Chemistry, Multidisciplinary
Johannes E. Erchinger, Reece Hoogesteger, Ranjini Laskar, Subhabrata Dutta, Carla Huempel, Debanjan Rana, Constantin G. Daniliuc, Frank Glorius
Summary: This article presents a new synthetic method that utilizes a photosensitizer to react sulfur fluoride compounds with alkenes, resulting in protected beta-amino sulfonyl fluorides. This method can be used to synthesize peptido sulfonyl fluorides, beta-ammonium sulfonates, and beta-sultams relevant in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Guangying Tan, Fritz Paulus, Alessia Petti, Maxim-Aleksa Wiethoff, Anna Lauer, Constantin Daniliuc, Frank Glorius
Summary: A novel radical relay 1,4-carboimination between two distinct olefins with alkyl carboxylic acid-derived bifunctional oxime esters was achieved via energy transfer catalysis. The reaction showed high chemo- and regioselectivity, forming multiple C-C and C-N bonds in a single operation. This mild and metal-free method exhibited a broad substrate scope and excellent tolerance of sensitive functional groups, providing easy access to structurally diverse 1,4-carboiminated products. Furthermore, the obtained imines could be readily converted into valuable biologically relevant free gamma-amino acids.
Article
Biochemistry & Molecular Biology
Yanjun Zheng, Tristan Wegner, Daniele Di Iorio, Marco Pierau, Frank Glorius, Seraphine V. Wegner
Summary: The nongenetic modification of cell membranes with proteins is a straightforward method in cellular engineering. A cholesterol analogue called CHIM-NTA has been developed for specific membrane immobilization of polyhistidine-tagged proteins, particularly in the liquid-ordered (Lo) domains. It can integrate into phase-separated giant unilamellar vesicles (GUVs) and live cell membranes, enabling the nongenetic modification of cell surfaces with proteins.
ACS CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Yujie Liang, Fritz Paulus, Constantin G. Daniliuc, Frank Glorius
Summary: We report a BF3-catalyzed [2 + 2] cycloaddition reaction between aldehydes and bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2-oxabicyclo[2.1.1]hexanes. A new BCB containing an acyl pyrazole group was discovered, which not only facilitates the reactions but also allows for diverse downstream transformations. Additionally, aryl and vinyl epoxides can be used as substrates that undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. These results will promote the exploration of complex sp(3)-rich bicyclic frameworks and BCB-based cycloaddition chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Yuquan Tong, Yeongju Lee, Xiaohui Liu, Jessica L. Childs-Disney, Blessy M. Suresh, Raphael I. Benhamou, Chunying Yang, Weimin Li, Matthew G. Costales, Hafeez S. Haniff, Sonja Sievers, Daniel Abegg, Tristan Wegner, Tiffany O. Paulisch, Elizabeth Lekah, Maison Grefe, Gogce Crynen, Montina Van Meter, Tenghui Wang, Quentin M. R. Gibaut, John L. Cleveland, Alexander Adibekian, Frank Glorius, Herbert Waldmann, Matthew D. Disney
Summary: Insufficient occupancy of the target, especially for RNA, leads to a lack of biological activity and the difficulty in recognizing RNA structures with small molecules adds to this challenge. By studying the molecular recognition patterns between a small-molecule collection and folded RNA structures, we can map the interaction landscapes across the human transcriptome and define structure-activity relationships. In cases where RNA-binding compounds bind elsewhere and are predicted to be biologically inert, an alternative strategy is to cleave the target through a ribonuclease-targeting chimera, using an RNA-binding molecule appended to a heterocycle that locally activates RNase L-1. Overlaying the substrate specificity of RNase L with the binding landscape of small molecules identifies potential bioactive binders that can be converted into degraders. Proof of concept is provided through the design of selective degraders for pre-miR-155, JUN mRNA, and MYC mRNA, demonstrating the potential of small-molecule RNA-targeted degradation as potent and specific modulators of RNA function.
Article
Nanoscience & Nanotechnology
Florian Bosse, Christian Gutheil, D. Thao Nguyen, Matthias Freitag, Mowpriya Das, Bonnie J. J. Tyler, Thorsten Adolphs, Andreas H. H. Schaefer, Heinrich F. F. Arlinghaus, Frank Glorius, Bart Jan Ravoo
Summary: Planar gold surfaces modified with N-heterocyclic carbene (NHC) were found to be more susceptible to wet chemical etching compared to undecorated areas. The selective decoration of NHCs on gold was achieved by microcontact printing, and the etching behavior could be tuned by changing the concentration of the NHC precursor. Surface patterning was confirmed by time-of-flight secondary-ion mass spectrometry and Kelvin probe force microscopy. The ability to selectively remove gold through surface ligand functionalization enables novel applications of NHCs in materials chemistry and nanofabrication.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Mowpriya Das, Markus Kohlstaedt, Maria Enders, Stephan Burger, Himadri Sekhar Sasmal, Birger Zimmermann, Andreas Schaefer, Bonnie J. Tyler, Heinrich F. Arlinghaus, Ingo Krossing, Uli Wuerfel, Frank Glorius
Summary: This study demonstrates the modification of ITO surface using N-heterocyclic carbenes (NHCs) precursor, IPr-CO2, via spin coating method. The modified ITO electrodes exhibit significantly reduced work function and provide high electron selectivity contacts in organic photovoltaic devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Multidisciplinary Sciences
Huamin Wang, Huiling Shao, Ankita Das, Subhabrata Dutta, Hok Tsun Chan, Constantin Daniliuc, K. N. Houk, Frank Glorius
Summary: In this study, a photoinduced ring enlargement method of thiophenes was developed, which involves the insertion of bicyclo[1.1.0]butanes to form eight-membered bicyclic rings under mild conditions. The synthetic value, broad functional-group compatibility, and excellent chemo- and regioselectivity were demonstrated by scope evaluation and product derivatization. Experimental and computational studies suggested a photoredox-induced radical pathway.
Article
Chemistry, Physical
Linda Quach, Egy Adhitama, Valentin Goeldner, Ankita Das, Feleke Demelash, Martin Winter, Uwe Karst, Tobias Placke, Frank Glorius
Summary: Film-forming electrolyte additives are crucial for the performance and safety of high-energy-density lithium-ion batteries. This study synthesized derivatives and conducted analyses to investigate the impact of molecular substrate parameters on battery performance. The research aims to enhance the fundamental understanding of influential substrate parameters and guide the design of electrolyte additives for high-energy-density lithium-ion batteries.
ACS APPLIED ENERGY MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Lukas Lueckemeier, Marco Pierau, Frank Glorius
Summary: This review aims to present the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes, highlighting recent advances and important trends, and providing a broad overview for the reader.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
Tristan Wegner, Anna L. L. Matos, Karine Porte, Kira Mehring, Marco Pierau, Hendrik Horstmeier, Volker Gerke, Frank Glorius
Summary: Cholesterol is a vital lipid in cellular membranes and plays a role in various cellular processes. Diseases like immunological disorders and cancer have been associated with abnormalities in cholesterol homeostasis. Thus, there is a need for molecular tools to study cholesterol distribution and interactions. In this study, a novel bifunctional imidazolium-based cholesterol analog (X-CHIM) was synthesized, which can serve as a versatile tool for investigating cellular cholesterol distributions and cholesterol-protein interactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Robert Zielinski, Mowpriya Das, Canan Kosbab, Mike Thomas Nehring, Mario Daehne, Norbert Esser, Martin Franz, Frank Glorius
Summary: The adsorption behavior of cyclohexyl cyclic (alkyl)(amino)carbene molecules on a silicon surface is investigated, showing a self-limited, well ordered growth of a stable monolayer with large domains, which is surprising on semiconductors. Additionally, the surface defect density strongly influences the grade of ordering, as the initial adsorption takes place on a defect site.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Florenz Buss, Mowpriya Das, Daniel Janssen-Mueller, Alexander Sietmann, Ankita Das, Lukas F. B. Wilm, Matthias Freitag, Michael Seidl, Frank Glorius, Fabian Dielmann
Summary: This study reports the synthesis and properties of photoswitchable electron-rich phosphines containing N-heterocyclic imines. Heteronuclear NMR spectroscopy and UV/vis studies reveal reversible electrocyclic ring-closing and ring-opening reactions of the imine substituents upon exposure to UV and visible light. The photoisomerization alters the electron-donating ability of the phosphines by up to Delta TEP = 8 cm-1.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tristan Wegner, Alexander Dombovski, Katrin Gesing, Alexander Koehrer, Matthias Elinkmann, Uwe Karst, Frank Glorius, Joachim Jose
Summary: The cell membrane is an important platform for modifying and manipulating cellular behavior. This study presents a method for functionalizing the bacterial membrane using lipid mimetics, allowing for a new type of cascade reaction.
