Article
Chemistry, Organic
Jiaping Wu, Baiyang Qian, Lili Lu, Haitao Yang, Yongjia Shang, Jitan Zhang
Summary: The study presents a concise method for synthesizing structurally diverse indoles using Rh-III catalysis to enable switchable C2 C-H olefination and alkylation of N-quinolinyl indoles with alkenes, as well as highly efficient C-H deuteration. The reaction can be conducted under practical conditions with a broad substrate scope and good tolerance towards various functional groups. The potential value of this synthetic methodology is demonstrated by the diverse late-stage modification of the products, providing a straightforward route to access functionalized indoles, especially indole-based P,N ligands.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Sif T. Linde, Vasco Corti, Vibeke H. Lauridsen, Johannes N. Lamhauge, Karl Anker Jorgensen, Nomaan M. Rezayee
Summary: This article presents a method for obtaining a versatile chiral biaryl structure through C-H halogenation reactions using high-valent Pd catalysis and chiral transient directing groups. The method is scalable, moisture and air insensitive, and in some cases, requires low Pd-loadings of only 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls can be prepared in high yield and excellent stereoselectivity, serving as building blocks for various reactions with orthogonal synthetic handles.
Article
Chemistry, Organic
Biplab Mondal, Subhadeep Hazra, Ayan Chatterjee, Manveer Patel, Jaideep Saha
Summary: This study developed a catalytic, reductive C-C bond formation method between alkenes and vinyl cyclopropane (VCP) through hydrogen atom transfer (MHAT). Despite the use of VCP as probes in radical-clock experiments, the translation of this method into synthetic methods for accessing elusive C-C bonds remains largely unexplored. This work represents the first exploration in this field, where the high chemoselectivity of MHAT for alkene over VCP was crucial for realizing the strategy. This method has a broad scope, high functional group tolerance, and useful applications.
Article
Chemistry, Multidisciplinary
Takanobu Saito, Joaquim Caner, Naoyuki Toriumi, Nobuharu Iwasawa
Summary: A novel method for the meta-selective C-H carboxylation of 1,1-diarylethylene derivatives using a rhodium catalyst and a stoichiometric reductant has been achieved. The introduction of a carboxyl group to the aryl ring at the meta-position was enabled with high selectivity. Both experimental and computational mechanistic studies indicate that a specific rhodium migration process plays a key role in this unusual aryl-to-aryl 1,2-rhodium shift.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Luo-Yan Liu, Zhoulong Fan, Md Emdadul Hoque, Shaoqun Qian, Guangrong Meng, Nikita Chekshin, Keita Tanaka, Jennifer X. X. Qiao, Kap-Sun Yeung, Jin-Quan Yu
Summary: Remote C-H functionalization of heterocyclic biaryls is crucial in synthesis and medicinal chemistry. New catalytic templates have been developed to functionalize the hindered ortho-C-H bonds of heterobiaryls, using directing heteroatom at the meta- or para-positions, with unprecedented site-selectivity. This protocol overcomes steric and electronic effects, allowing olefination of sterically hindered heterobiaryls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Maorui Wang, Chengqian Zhang, Chenggang Ci, Huanfeng Jiang, Pierre. H. Dixneuf, Min Zhang
Summary: Despite the challenges, we have successfully developed a room temperature approach for the direct construction of alpha-hydroxyalkyl cyclic amines through the strategy of electroreductive alpha-hydroxyalkylation. This method offers a broad substrate scope, simplicity in operation, high chemoselectivity, and does not require pressurized H2 gas or transition metal catalysts. The activation of reactants by the zinc ion generated from anode oxidation plays a crucial role in this transformation. This strategy, combined with substrate activation by Lewis acids, is expected to lead to the development of more useful transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Guoshuai Li, Yifei Yan, Pengfei Zhang, Xiaohua Xu, Zhong Jin
Summary: A new palladium-catalyzed meta-selective C-H olefination of aromatic carbonyl compounds was achieved by utilizing noncovalent hydrogen-bonding interaction directed by engineered N,N'-substituted ureas, demonstrating site-selective control without the need for prior stoichiometric installation and removal of directing groups.
Article
Chemistry, Organic
Kelin Wang, Xia Song, Yongdi Xin, Xinying Zhang, Xuesen Fan
Summary: In this study, a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives was achieved via cascading reactions of N-nitrosoanilines with iodonium ylides. The formation mechanisms of the products were elucidated, and the developed protocols demonstrated easily controllable selectivity, mild reaction conditions, a clean and sustainable oxidant (air), and structurally diverse valuable products. Furthermore, the utility of the products was showcased by their facile and diverse transformations into synthetically and biologically interesting compounds.
Article
Chemistry, Applied
Jinyuan Jiang, Jidan Liu, Zhenke Yang, Liyao Zheng, Zhao-Qing Liu
Summary: A one-pot three-component synthesis of benzofuran-3(2H)-ones with tetrasubstituted carbon stereocenters has been successfully developed via Rh(III)-catalyzed C-H/C-C bond activation and cascade annulation, using salicylaldehydes, cyclopropanols, and alkyl alcohols as starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Yangyang Wang, Xiaobo Xu, Binghan Pang, Liqiang Hao, Gaorong Wu, Yafei Ji
Summary: In this study, the palladium-catalyzed sequential C(sp(3))-H and C(sp(2))-H bond diolefination reaction of o-toluidine was achieved using acetyl-protected aminoethyl phenyl thioether ligands. This novel reaction allows for the preparation of conjugated diene structure via an immediate second olefination, based on the first C(sp(3))-H olefination, in one pot. Various triflyl-protected anilines and acrylates were elegantly used as coupling partners. Furthermore, the unpurified diolefination products can be easily converted to tetrahydroquinoline derivatives.
Article
Chemistry, Multidisciplinary
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An Chen
Summary: Transition metal catalyzed decarbonylation offers a unique synthetic strategy for new chemical bond formation. The study developed a visible light induced rhodium catalysis for decarbonylative coupling of imides with alkynes under ambient conditions, revealing the rhodium complex serves as both the catalytic center and photosensitizer. This visible light promoted catalytic decarbonylation strategy opens up new opportunities for re-evaluating old transformations with ligand dissociation as a rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Liselle Atkin, Daniel L. Priebbenow
Summary: Investigations revealed that the indenyl-derived catalyst significantly accelerated the directed ortho C-H amidation of benzoyl silanes using 1,4,2-dioxazol-5-ones. The slippage of the indenyl complex enables ligand substitution at the metal center to proceed via associative pathways, leading to rate and yield enhancements. Interestingly, this phenomenon is specific for weakly coordinating carbonyl-based directing groups, with no acceleration observed for nitrogen-based directing groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, Multidisciplinary
Xuefeng Tan, Leonardo Massignan, Xiaoyan Hou, Johanna Frey, Joao C. A. Oliveira, Masoom Nasiha Hussain, Lutz Ackermann
Summary: The rhodium bimetallic electrocatalytic system enables arene C-H oxygenation by weakly coordinating amides and ketones, leading to selective dihydrooxazinone synthesis through twofold C-H functionalization. Mechanistic studies using experiment, mass spectroscopy, and cyclovoltammetric analysis support an unprecedented electrooxidation-induced C-H activation in the bimetallic rhodium catalysis manifold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Shrikant M. Khake, Naoto Chatani
Summary: The Rh(III)-catalyzed reaction of aniline derivatives containing a pyrimidine directing group with vinylsilanes leads to the formation of C3-substituted indoline derivatives via a highly regioselective C-H activation/alkene cyclization cascade. Mechanistic experiments suggest that C-H bond cleavage is not the rate-determining step, but rather the reaction proceeds through the formation of a six-membered rhodacycle as a key catalytic species via pyrimidine-directed electrophilic ortho-C-H rhodation.
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)
Editorial Material
Chemistry, Organic
Floris Buttard, Tatiana Besset
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)
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
Jordan Vigier, Melissa Gao, Philippe Jubault, Helene Lebel, Tatiana Besset
Summary: A photoinduced selective synthesis of thiocyanate and isothiocyanate derivatives from readily available carboxylic acids was developed using N-thiocyanatosaccharin and a catalytic amount of base or acid. This molecular editing strategy allowed for the functionalization of bioactive compounds. Additionally, a divergent process for the catalytic decarboxylative thiocyanation and isothiocyanation of alkyl carboxylic acids promoted by visible light was developed.
CHEMICAL COMMUNICATIONS
(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.
