Review
Chemistry, Physical
Sourav Sekhar Bera, Michal Szostak
Summary: This comprehensive review presents catalytic methods utilizing cobalt-NHC complexes, focusing on catalyst structure, the role of the NHC ligand, properties of the catalytic system, mechanism, and synthetic utility. The survey suggests that well-defined cobalt-NHC catalysts have great potential in the design and application of catalytic reactions using more abundant 3d transition metals.
Article
Chemistry, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Planer, Jenni Frosch, Marvin Koneczny, Damian Trzybinski, Krzysztof Wozniak, Karol Grela, Matthias Tamm
Summary: This study explores the use of lithium complexes with weakly coordinating borate moieties for the preparation of silver(I) or copper(I) WCA-NHC complexes. Reactions in different solvents and with different metals are investigated, revealing various transformations during the process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Wioletta Kosnik, Dawid Lichosyt, Marcin Sniezek, Angelika Janaszkiewicz, Krzysztof Wozniak, Maura Malinska, Bartosz Trzaskowski, Anna Kajetanowicz, Karol Grela
Summary: The formation of sterically hindered C-C double bonds through catalytic olefin metathesis is a challenging task for Ru catalysts. To overcome this limitation, a new NHC ligand was designed, which reduced the susceptibility of small-size NHC catalysts to decomposition. The resulting isomeric complexes exhibited similar high thermodynamic stability but different application profiles in catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
G. Mahantesh, Deepika Sharma, Rambabu Dandela, Vasudevan Dhayalan
Summary: This article reviews the synthesis and properties of N-heterocyclic olefins (NHO), as well as their applications as catalysts in organic synthesis. NHOs display electron-rich and polar characteristics, as well as strong basicity, making them highly promising catalysts with great chemical potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Biochemistry & Molecular Biology
Abdollah Neshat, Piero Mastrorilli, Ali Mousavizadeh Mobarakeh
Summary: Since the discovery of persistent carbenes, the design and applications of this class of ligands and their metal complexes have rapidly grown. N-heterocyclic carbenes (NHCs) have become popular among chemists due to their modular synthesis and adjustability. The strength of the metal-carbon bond in transition metal complexes bearing NHCs depends on the energy match between the NHC ligand and the metal ion. NHC ligands have been explored with both transition metals and main group elements. The catalytic applications of NHC ligands linked with a second tether have been extensively studied, with carbon-carbon coupling reactions, transfer hydrogenation, ketone hydrosilylation, and chiral catalysis being among the most popular reactions. Areas such as CO2 reduction and C-H borylation have received less attention. The synthesis and applications of transition metal complexes are also covered.
Article
Chemistry, Applied
Angelina Mary, Nimisha Jain, Rahul Sakla, D. Amilan Jose, Bhagwan Sahai Yadav, Abbas Raja Naziruddin
Summary: This article presents the syntheses of ruthenium (II) complexes with an N-heterocyclic carbene (NHC)-based C and N donor set and an -NCS ligand, and evaluates their use as photosensitizers in dye-sensitized solar cells (DSSCs). Results show that the complexes without a phenyl spacer between the acid anchor and the tpy effectively absorb visible light and have higher photon conversion efficiency (PCE) in DSSCs.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Hilke Burmeister, Pascal Dietze, Lutz Preu, Julia E. Bandow, Ingo Ott
Summary: Ruthenium(II) NHC complexes exhibited stronger antibacterial effects compared to metal-free benzimidazolium cations, particularly against Gram-positive bacteria. The inhibition of bacterial thioredoxin reductase by selected complexes suggested a potential contributing factor to their antibacterial effects.
Review
Biochemistry & Molecular Biology
Vincent Ritleng, Christophe Michon
Summary: This review focuses on the application of ruthenium complexes with bidentate donor-functionalized N-heterocyclic carbene ligands in catalyzing hydrogen transfer reactions, and discusses the effects of different donor atoms and carbene ligands on the transfer hydrogenation reactions. This research is important for improving the efficiency and selectivity of catalytic hydrogen transfer reactions.
Article
Chemistry, Multidisciplinary
Yuan-Yuan Xu, Zhong-Hua Gao, Cao-Bo Li, Song Ye
Summary: The enantioselective alpha-oxidative coupling of enals with carboxylic acids was achieved by umpolung of an NHC-bound enolate with an iodine(III) reagent. The reaction produced alpha-acyloxyl-beta,gamma-unsaturated esters in good yields, with high regio- and enantioselectivities. The reaction involved the formation of an enol iodine(III) intermediate from the enolate with iodosobenzene, which changed the polarity of the enal's alpha-carbon from nucleophilic to electrophilic and facilitated the subsequent carboxylate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yaru Jing, Jiahao Liu, Zongren Ye, Jiaqi Su, Yan Liu, Zhuofeng Ke
Summary: This study systematically investigates the unprecedented cooperation roles of NHC and CO ligands in N-heterocyclic carbene manganese complex promoted CO2 hydrogenation to formate. The results demonstrate the important cooperation role of the CO ligand in stabilizing the negatively charged hydride and assisting the reaction. The study provides important mechanistic insights into the rational design of bifunctional catalysts with conventional innocent ligands by uncovering the significant cooperation role of the often neglected CO ligand.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Lilia Longo, Somayeh Taghavi, Elena Ghedini, Federica Menegazzo, Alessandro Di Michele, Giuseppe Cruciani, Michela Signoretto
Summary: This study focuses on the development of sustainable and efficient catalysts for the selective hydrogenation of HMF to HHD using Ru supported on activated biochars. Activated biochars derived from different biomasses show distinct properties, with A(HSw) displaying better trapping and anchoring of Ru nanoparticles, leading to higher catalytic activity.
Article
Biochemistry & Molecular Biology
Stefan Czarnocki, Louis Monsigny, Michal Sienkiewicz, Anna Kajetanowicz, Karol Grela
Summary: A modular and flexible strategy for synthesizing N-heterocyclic carbene (NHC) ligands bearing Bronsted base tags has been proposed and used to prepare two tagged NHC ligands with different acid residues. These tagged NHC ligands serve as an attractive starting point for the synthesis of olefin metathesis ruthenium catalysts with non-dissociating ligands. The impact of the Bronsted base tags on the activity of the obtained olefin metathesis catalysts has been investigated.
Article
Chemistry, Inorganic & Nuclear
Lingyu Kong, Yajie Chou, Muriel Albalat, Marion Jean, Nicolas Vanthuyne, Stephane Humbel, Paola Nava, Herve Clavier
Summary: The concept of atropisomeric N-heterocyclic carbene (NHC)-metal complexes with C-2-symmetry was extended to palladium-based complexes. Through a comprehensive study of NHC precursors and screening of various NHC ligands, the formation of meso complexes was successfully circumvented. Eight atropisomeric NHC-palladium complexes were prepared and obtained with high enantiopurities through efficient chiral HPLC resolution. These complexes demonstrated good activity in the intramolecular alpha-arylation of amides, leading to the isolation of cyclic products with excellent enantioselectivities (up to 98% ee).
DALTON TRANSACTIONS
(2023)
Article
Infectious Diseases
Jessica Ceramella, Rubina Troiano, Domenico Iacopetta, Annaluisa Mariconda, Michele Pellegrino, Alessia Catalano, Carmela Saturnino, Stefano Aquaro, Maria Stefania Sinicropi, Pasquale Longo
Summary: Ruthenium N-heterocyclic carbene (Ru-NHC) complexes were designed, synthesized, and evaluated for their biological activities. The complexes displayed significant anticancer activity against triple-negative human breast cancer cell lines MDA-MB-231. They also showed potent antibacterial activity against Gram-positive bacteria Staphylococcus aureus and strong antioxidant ability.
Article
Chemistry, Physical
Justin Dubbert, Marco Valtolina, Alexander Huber, Tim D. Scherz, Christoph Woelper, Constantin G. Daniliuc, Ofer Filiba, Saumik Sen, Igor Schapiro, Fabio Rizzo, Jens Voskuhl
Summary: In this study, a series of chlorinated bridged ethers with varying numbers of sulfur and oxygen atoms were synthesized and their tunable photophysical properties in different aggregated states were investigated.
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
Chemistry, Multidisciplinary
Max Wienhold, Byeongseok Kweon, Calum McLaughlin, Matthias Schmitz, Till J. B. Zaehringer, Constantin G. Daniliuc, Christoph Kerzig, Ryan Gilmour
Summary: Amide groups are widely present in the chemical space continuum, and their structural and pharmacological importance as well as hydrolytic vulnerabilities drive the development of bioisosteres. Alkenyl fluorides have a long history as effective mimics, but emulating peptide bond isomerization with fluoro-alkene surrogates is challenging. This study presents a design of an ambiphilic linchpin that enables isomerization process, providing geometrically-programmable building blocks for small molecule amide and polyene isostere discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Maurice Dellin, Ina Rohrbeck, Purva Asrani, Julian A. Schreiber, Nadine Ritter, Frank Glorius, Bernhard Wuensch, Thomas Budde, Louisa Temme, Timo Struenker, Birgit Stallmeyer, Frank Tuettelmann, Sven G. Meuth, Marc Spehr, Johann Matschke, Andrea Steinbicker, Christos Gatsogiannis, Raphael Stoll, Nathalie Strutz-Seebohm, Guiscard Seebohm
Summary: The study identified two binding sites, PS1 and S0, for PI(3,5)P-2 on the KCNQ1/KCNE1 channel, and found that binding of PI(3,5)P-2 to both sites is necessary for stabilizing the channel's open state.
BIOLOGICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chaohuang Chen, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The neutral N-heterocyclic carbene stabilized boranotsignalkene 1, prepared by a BH borenium/hydroboration method, can form stable copper, gold, or palladium pi-complexes. The polar boranotsignalkene B=C system undergoes selective hydroboration reactions with (C6F5)(2)BH or C6F5BH2 center dot SMe2 boranes. The latter reaction involves subsequent rearrangement leading to the exchange of internal hydride and isothiocyanate substituents at the borane pair.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Dawod Yousif, Luca Vaghi, Constantin G. Daniliuc, Riccardo Po, Antonio Papagni, Fabio Rizzo
Summary: The regioselective nitration of 9,9'-spirobifluorene under mild conditions is reported for the first time using Menke's and Crivello's conditions. The optimized protocol yields 2-nitro and 2,2'-dinitro-9,9'-spirobifluorene in 79% and 95% yield, respectively, and for the first time, 2,2',7-trinitro-9,9'-spirobifluorene with a yield of 66%. Additionally, the role of dinitrate salt in Crivello's protocol has now been clarified, opening up new possibilities in the preparation of functional materials.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Joel Haefliger, Louise Ruyet, Nico Stuebke, Constantin G. Daniliuc, Ryan Gilmour
Summary: In this article, a cascade reaction is validated to generate novel gem-difluorinated isosteres from 1,3-diaryl cyclobutanols in a single operation, utilizing the biological significance of partially saturated, fluorine-containing rings and the physicochemical advantages conferred by fluorination.
NATURE COMMUNICATIONS
(2023)
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, 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
Chemistry, Physical
Dasharath Kondhare, Xenia Heddinga, Simone Budow-Busse, Constantin Daniliuc, Frank Seela
Summary: The single-crystal X-ray structure of 5-aza-7-deaza-7-iodoguanine 2'-C-methylribonucleoside 1 is described, which was synthesized through stereoselective nucleobase anion glycosylation and subsequent deprotection. The CD-spectrum analysis of 1 revealed the significant impact of the iodo substituent on the molecule. A dye conjugate was generated by Suzuki-Miyaura cross-coupling of 1 with pyrene boronic acid, showing solvent dependent exciplex fluorescence.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Fritz Paulus, Colin Stein, Corinna Heusel, Tobias J. Stoffels, Constantin G. Daniliuc, Frank Glorius
Summary: In this study, a novel three-component 1,2,5-trifunctionalization reaction driven by visible light energy transfer-catalysis was reported. Selective installation of three different functional groups was achieved in one step by utilizing imine-based bifunctional reagents and two distinct alkenes. Mechanistic studies and downstream modifications demonstrated the synthetic utility of the obtained products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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.
