Article
Chemistry, Applied
Marina Godino-Ojer, Sergio Morales-Torres, Francisco J. Maldonado-Hodar, Elena Perez-Mayoral
Summary: Transition metal-carbon aerogels, such as Mo, Fe, Co, or Cu, serve as effective and selective catalysts for the synthesis of quinoxalines 1 from o-phenylenediamine 2 and α-hydroxy ketones 3, presenting a sustainable alternative to other carbon-based catalysts or MOFs. The doping metal phase, which consists of metal oxides or zero-valent metals, along with the metal loading at the carbon aerogel surface, plays a crucial role in determining the reactivity and selectivity of the catalysts. The Mo-500 catalyst exhibits the highest efficiency and selectivity, likely working through the initial oxidation of α-hydroxy ketones followed by condensation-dehydration reactions.
Review
Chemistry, Physical
Bernhard J. Gregori, Mattis-Ole W. S. Schmotz, Axel Jacobi von Wangelin
Summary: This article introduces the application of 3d metal catalysts in alkyne semi-hydrogenation, focusing on their groundbreaking advances in stereoselectivity.
Review
Chemistry, Physical
Bruno Mattia Bizzarri, Angelica Fanelli, Lorenzo Botta, Claudio Zippilli, Silvia Cesarini, Raffaele Saladino
Summary: Dendrimers are highly branched structures with a defined shape, dimension, and molecular weight, consisting of a central core, branches, and terminal groups. They have been widely studied and applied in various fields, including catalytic organic and inorganic processes, sustainable and low environmental impact, photosensitive materials, nano-delivery systems, and antiviral agents.
Article
Chemistry, Multidisciplinary
Fabrice Gallou, Harald Groeger, Bruce H. Lipshutz
Summary: Biocatalytic processes and chemoenzymatic catalysis are attractive to fine chemical companies due to their selective and environmentally friendly nature. Integration of chemocatalysis and biocatalysis in aqueous media allows for more efficient processes. However, industrial usage is currently variable.
Article
Chemistry, Applied
Artur Braun, Debajeet K. Bora, Lars Lauterbach, Elisabeth Lettau, Hongxin Wang, Stephen P. Cramer, Feipeng Yang, Jinghua Guo
Summary: This article discusses the importance of the 100th anniversary of CASALE SA, a leading nitrogen fixation technology developer, and solutions for sustainable ammonia production. The article reviews the role of nitrogen in photosynthesis and biology, as well as the use of ammonia as fertilizer and an energy carrier. It also introduces novel analytical techniques and provides real-world examples of ammonia production and usage.
Review
Chemistry, Inorganic & Nuclear
Han Peng, Vincent Ritleng, Christophe Michon
Summary: This article reviews the development of supported Noyori-Ikariya catalysts based on ruthenium, rhodium, and iridium for asymmetric transfer hydrogenation and related tandem reactions over the past 7 years. It highlights and discusses the synthesis, reactivity, and recycling of these catalysts.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Chemistry, Physical
Shengnan Lin, Tingan Zhang
Summary: This paper focuses on the synthetic methods of metal spinel oxides (MSOs) and their applications in adsorption catalysis, magnetic materials, electrodes, and sensors. The modifications and applications of AB2O4 (M > 2, B = Al, Fe, Co, and Mn) MSOs are compared. The advantages and disadvantages of MSO synthetic methods are briefly introduced and discussed. The future development trends and application extensions for MSO syntheses are also discussed.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Chemistry, Organic
Satya Prakash Panda, Sudhir Kumar Hota, Rupashri Dash, Lisa Roy, Sandip Murarka
Summary: In this study, a transition-metal-free NaI/PPh3-mediated direct C-H alkylation of azauracils using N-(acyloxy)-pthalimides (NHPIs) as alkyl surrogates was developed under visible light irradiation. Mechanistic studies revealed the formation of a photoactivated electron donor-acceptor (EDA) complex between NaI/PPh3, TMEDA, and alkyl NHPI ester, and the crucial role of TMEDA in enhancing the activity of the photoredox system. This reaction demonstrated a wide scope, scalability, and good functional group tolerance, allowing for the alkylation of various azauracils with primary, secondary, and tertiary NHPI esters under mild conditions to afford the desired products in good to excellent yields.
Review
Chemistry, Multidisciplinary
Ye Run-Ping, Wang Xinyao, Cameron-Alexander Hurd Price, Liu Xiaoyan, Yang Qihua, Mietek Jaroniec, Liu Jian
Summary: This work discusses the preparation and properties of special catalyst YCSNs in heterogeneous hydrogenation reactions, as well as the challenges in their application in gas and liquid-phase hydrogenation reactions, and explores the opportunities and prospects for future research.
Article
Chemistry, Multidisciplinary
Claudia E. Berdugo-Diaz, Melissa T. Manetsch, Yang Sik Yun, Jieun Lee, Jing Luo, Xue Chen, David W. Flaherty
Summary: Esters can be reduced to ethers and alcohols through C-O bond cleavage by hydrogenation and hydrogenolysis pathways on Bronsted acidic faujasite (M-FAU) supported metal nanoparticles. The rates and selectivities of each pathway are influenced by the metal identity (M=Co, Ni, Cu, Ru, Rh, Pd, and Pt). Pt-FAU catalyst exhibits propyl acetate consumption rates up to 100 times higher than other M-FAU catalysts and achieves a 34% selectivity for ethyl propyl ether. The reduction of esters appears to involve a bifunctional mechanism, with stepwise addition of H* atoms to the carbonyl to form hemiacetals on the metal sites, followed by hemiacetal diffusion to Bronsted acid sites for dehydration to ethers or decomposition to alcohol and aldehyde. The reduction rates of propyl acetate seem to be determined by H* addition to the carbonyl and C-O cleavage of hemiacetal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Yichen Wu, Peng Wang
Summary: Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry. Monohydrosilanes, which bear a Si-H bond, are especially unique due to their facile transformations through stereospecific bond-formation reactions. In addition, they have also been used as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, and potential optoelectronic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Multidisciplinary Sciences
Chiara Costabile, Stefania Pragliola, Fabia Grisi
Summary: The last decades have witnessed the rapid growth of applications of N-heterocyclic carbenes (NHCs) in various chemistry fields. Due to their unique properties, NHCs have become a powerful tool in coordination chemistry, particularly in the synthesis of stable metal-ligand frameworks with main group metals and transition metals. This article provides an overview of the use of five-membered monodentate C-2-symmetric N-heterocyclic carbenes (NHCs) as ligands for transition-metal complexes and highlights their most relevant applications in asymmetric catalysis.
Review
Chemistry, Multidisciplinary
Risto Savela, Carolina Mendez-Galvez
Summary: Isoindolinone structure is an important privileged scaffold found in a large variety of naturally occurring as well as synthetic, biologically and pharmaceutically active compounds. Synthetic methodologies for accessing this heterocyclic skeleton have received significant attention during the past decade, with two main categories of strategies identified.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Reka Adamik, Balazs Buchholcz, Ferenc Darvas, Gellert Sipos, Zoltan Novak
Summary: This review provides a conceptual and critical summary of micellar synthesis possibilities that are well suited to DEL synthesis, as well as discussion of existing examples of micellar DEL approaches and selection of micellar organic transformations fundamentally suitable for DEL.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yanhua Hu, Yashi Zou, Huiwen Yang, Haotian Ji, Yue Jin, Zhenfeng Zhang, Yangang Liu, Wanbin Zhang
Summary: Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph-BPE-Co-I catalyst for the precise synthesis of chiral Z-allylamides with high activity and excellent enantioselectivity. The difference in catalytic activity between cobalt complexes of Ph-BPE and QuinoxP* was explained by the process decomposition of rate-determining step in the second hydrogenation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Naba Abuhafez, Antoine Perennes, Rafael Gramage-Doria
Summary: This review article describes the recent advances in supramolecular catalysis involving metalloporphyrins as substrate recognition sites in the second coordination sphere of the catalyst. Inspired by host-guest phenomena, these catalytic systems exhibit unique activities, selectivities, and modes of action that are difficult to achieve using purely covalent strategies.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Matthieu Jouffroy, Thi-Mo Nguyen, Marie Cordier, Marielle Blot, Thierry Roisnel, Rafael Gramage-Doria
Summary: Direct reductive amination (DRA) is a widely used reaction in organic chemistry, aiming to convert carbonyl groups and amines into aminated compounds. The conventional method involves the use of a super stoichiometric amount of hazardous hydride reagents, which is incompatible with many sensitive functional groups. This study presents a new DRA method using iridium catalysis, overcoming the limitation of ketones with 2 degrees amines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Editorial Material
Chemistry, Multidisciplinary
Matthieu Jouffroy, Thi-Mo Nguyen, Marie Cordier, Marielle Blot, Thierry Roisnel, Rafael Gramage-Doria
Summary: This issue features an Ir-based catalytic system fueled by hydrogen for the direct reductive amination of ketones and secondary amines, allowing the preparation of complex aliphatic tertiary amines and expanding the chemical space.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Michele Tomasini, Lucia Caporaso, Jonathan Trouve, Jordi Poater, Rafael Gramage-Doria, Albert Poater
Summary: This study presents a non-biological catalyst that binds substrates via the induced fit model, with features reminiscent of enzymes. The research also reveals new elementary catalytic steps.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Purushothaman Rajeshwaran, Jonathan Trouve, Khalil Youssef, Rafael Gramage-Doria
Summary: The Wacker reaction is a significant industrial transformation that oxidizes olefins to ketones. However, it typically requires expensive palladium catalysts, which has led to the development of Wacker-type processes that avoid their use, allowing for more sustainable procedures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Thalita S. Galhardo, Anderson K. Ueno, Thais A. Costa-Silva, Andre G. Tempone, Wagner A. Carvalho, Cedric Fischmeister, Christian Bruneau, Dalmo Mandelli, Joao Henrique G. Lago
Summary: In this study, compounds isolated from N. leucantha were used as starting material to synthesize two new derivatives, which showed activity against trypanosome and no toxicity to mammalian cells. Mechanism study revealed that the derivatives caused depolarization of the parasite's plasma membrane and collapse of mitochondrial membrane potential. Therefore, this compound could be a potential candidate for future drug design in the treatment of Chagas disease.
CHEMICO-BIOLOGICAL INTERACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Yang Sun, Kais Dhbaibi, Hortense Lauwick, Claudia Lalli, Gregory Taupier, Yann Molard, Rafael Gramage-Doria, Sylvie Derien, Jeanne Crassous, Mathieu Achard
Summary: A novel enantiopure pi-allylruthenium(IV) precatalyst was used for the enantioselective and stereospecific allylations of indoles, resulting in the synthesis of indolin-3-ones with vicinal stereogenic centers. The separation of diastereoisomers that exhibited opposite circularly polarized luminescence (CPL) activities in various solvents, including water, highlighted the potential of these sustainable transformations and the newly synthesized molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Erwan Prignot, Chanjuan Zhang, Olivier Jeannin, Zakaria Halime, Rafael Gramage-Doria, Franck Camerel
Summary: Metal-bis(dithiolene) complexes derived from Ni(II), Co(II), Pd(II), Pt(II) and Au(III) have been synthesized and characterized. Co(II) species are found to be dimeric in both solid state and solution, while Ni(II), Pd(II), Pt(II) and Au(III) coordination complexes exhibit monomeric structures. These metal-bis(dithiolene) complexes are highly stable in solution and retain their square planar geometry even when bound by pyridine derivatives.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Rafael Gramage-Doria
Summary: In order to obtain new supramolecular ligands built around a zinc-porphyrin scaffold, we attempted to access sulfonyl triazole intermediates through copper-catalyzed click reactions. Unexpectedly, the presence of the zinc-porphyrin moiety prevents the formation of these triazole intermediates. Instead, the copper catalyst undergoes a different reaction pathway, reacting with trace amounts of alcohols or water in the media, leading to the formation of sulfonyl imidates or sulfonyl amides covalently connected to the zinc-porphyrin. Our study shows that copper-catalyzed click reactions can follow different mechanisms when occurring in close proximity to a zinc-porphyrin unit, which acts as a Lewis acid to stabilize otherwise inaccessible reaction intermediates.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Physical
Chanjuan Zhang, Erwan Prignot, Olivier Jeannin, Antoine Vacher, Diana Dragoe, Franck Camerel, Zakaria Halime, Rafael Gramage-Doria
Summary: In this study, nonionic dimeric cobalt-dithiolene complexes on a multiwall carbon nanotube/carbon paper electrode were shown to be efficient electrocatalysts for hydrogen production in aqueous media at pH 7. The high turnover numbers and increased cobalt concentration on the modified electrode suggest that immobilizing low-cost metal complexes on carbon material is a promising strategy for designing highly electroactive electrodes for green energy production.
Article
Chemistry, Organic
Yu-Chao Yuan, Qiu-Li Lu, Xiao-Tong Zhu, Sergio Posada-Perez, Miquel Sola, Albert Poater, Thierry Roisnel, Rafael Gramage-Doria
Summary: Selective C-H functionalization for the formation of C-N bonds is crucial in organic synthesis. A highly reactive ruthenium-based catalytic system utilizing biologically-relevant cyclic amides as weak directing groups is reported, showing excellent levels of selectivity. The use of dioxazolone derivatives as amidating reagents overcomes issues encountered with unstable azide derivatives and allows for reactions under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Jonathan Trouve, Khalil Youssef, Sitthichok Kasemthaveechok, Rafael Gramage-Doria
Summary: Iron catalysts enable Markovnikov-selective reactions, achieving up to 99% selectivity for ketone products from (hetero)aromatic and aliphatic olefins under ambient conditions. The catalyst design, inspired by the promiscuous activity of cytochromes P-450 enzymes, allows the formation of iron-hydride species under catalytically relevant conditions, leading to the desired selectivity.
Article
Chemistry, Organic
Kamil Kupietz, Jonathan Trouve, Thierry Roisnel, Samia Kahlal, Rafael Gramage-Doria
Summary: In this study, a novel bis-zinc-porphyrin compound with two macrocycles covalently connected by a short buta-1,3-diyne linkage was synthesized. The unexpected formation of this compound was explained by control experiments and an improved synthesis was achieved under copper-catalyzed Glaser-Hay coupling reaction conditions. This highly sterically congested bis-zinc-porphyrin derivative exhibited supramolecular host behavior and could encapsulate ditopic molecular guests with a high association constant.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Thalita S. Galhardo, Anderson K. Ueno, Wagner A. Carvalho, Thais A. Costa-Silva, Marina M. Goncalves, Mariana B. Abiuzi, Andre G. Tempone, Joao Henrique G. Lago, Dalmo Mandelli, Cedric Fischmeister, Christian Bruneau
Summary: Ruthenium-catalyzed cross metathesis of biseugenol with electron-deficient olefins resulted in the synthesis of derivatives 3a-3e in good yields and excellent conversion rates. The antitrypanosomal activity of these compounds against Trypanosoma cruzi was evaluated, and compounds 3b and 3d showed similar IC50 values to biseugenol, but with reduced toxicities and similar selectivity indexes to the standard drug benznidazol.
Article
Chemistry, Multidisciplinary
Ludivine Poyac, Stefano Scoditti, Xavier Dumail, Michel Granier, Sebastien Clement, Rafael Gramage-Doria, Charles H. Devillers, Sebastien Richeter
Summary: The electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. It was found that when porphyrins are used as NHC-wingtips, the catalytic activity of the neighboring NHC-Rh(I) complex in the conjugate addition reaction is significantly improved.
CHEMICAL COMMUNICATIONS
(2022)
