Review
Chemistry, Inorganic & Nuclear
Hui Jin, Yujiao Sun, Zejun Sun, Meng Yang, Rijun Gui
Summary: In recent years, there has been a growing interest in scientific research on zero-dimensional (0D) sulfur nanomaterials, focusing on sulfur nanoparticles, sulfur quantum dots, and various nanosulfur-containing functional materials. Various synthetic methods, modification strategies, and versatile applications of 0D sulfur nanomaterials have been systematically summarized in this review. The review also evaluates the current advances, challenges, and future prospects in the field, aiming to promote the development of 0D nanomaterials and explore new low-dimensional functional nanomaterials for promising applications.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Organic
Radell Echemendia, Kleber T. de Oliveira, Antonio C. B. Burtoloso
Summary: A novel visible-light-promoted coupling of diazoketones with sulfoxonium ylides, employing a violet light-emitting diode, is described under both batch and continuous flow conditions. This transformation permits the direct synthesis of synthetically useful 1,3-dicarbonyl sulfoxonium ylides.
Article
Chemistry, Organic
Jagadeesh Reddy Thondur, Duddu S. Sharada, Gedu Satyanarayana
Summary: A unique, facile, and straightforward electrochemical oxidative annulation of inactivated propargyl aryl ethers with sulfonyl hydrazides leading to 3-sulfonated 2H-chromenes has been achieved. This green protocol works under mild reaction conditions using a constant current in an undivided cell and is devoid of oxidants and catalysts. The process exhibited a broad scope and functional group tolerance, providing an alternative and sustainable strategy for conventional chromene synthesis.
Article
Multidisciplinary Sciences
Peiyao Yan, Wei Zhao, Fiona McBride, Diana Cai, Joseph Dale, Veronica Hanna, Tom Hasell
Summary: Inverse vulcanization is a process to convert sulfur into polymers. This study presents a synthetic method of inverse vulcanization via mechanochemical synthesis, which allows for a broader range of monomers and yields materials with enhanced mercury capture capacity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Zhenbo Guo, Ruifeng Wang, Yuanyi Guo, Jiawei Jiang, Zhiqiang Wang, Wei Li, Minghui Zhang
Summary: This study synthesized PdmPn/CNF catalysts with different crystal phases and systematically studied their sulfur resistance. The results showed that Pd5P2/CNFs exhibited the best hydrogenation activity under sulfur poisoning conditions, and the weakening of sulfur-related bonds led to the difficulty in forming palladium sulfide.
Article
Chemistry, Organic
Shuangrong Liu, Zhimin Ying, Qi Zhu, Xiuwen Zhong, Jie Cen, You Wu, Yongping Yu, Jiaan Shao, Wenteng Chen
Summary: This study reveals a step-economical nitrite-triggered cycloaddition reaction for the modular assembly of isoxazoles (or isoxazolines) from bromide and alkyne/alkene. The reaction offers high regio-selectivity, excellent efficiency, wide functionality tolerance, biocompatible conditions, and operational simplicity, making it suitable for the direct diversification of pharmaceuticals and bio-relevant motifs.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Michal Tryniszewski, Dariusz Basiak, Michal Barbasiewicz
Summary: Methanedisulfonyl fluoride can convert aromatic aldehydes into useful substrates and mimic the mechanism of Horner-Wadsworth-Emmons olefination. In the absence of base, electron-rich aldehydes can also undergo Knoevenagel condensation to yield unsaturated 1,1-disulfonyl fluorides. Additionally, elusive ethene-1,1-disulfonyl fluoride can be trapped with 4-(dimethylamino)pyridine to form a zwitterionic adduct as characterized by X-ray studies.
Review
Biochemistry & Molecular Biology
Mehdi Jaymand
Summary: Starch is a widely used natural polymer with various applications. However, native starch suffers from drawbacks that require modifications. Chemical approaches, particularly the incorporation of sulfur functionality-containing groups, have been proven to enhance physicochemical and biological properties.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2022)
Article
Chemistry, Physical
Rui Du, Zhangyan Shi, Chuanbai Yu, Wenhui Rao, Chengying Xu, Jiangle Wang
Summary: Graphene oxide was synthesized successfully using a modified hummers method and graphene oxide/sulfur composites were then prepared via melt diffusion method to enhance the performance of lithium-sulfur batteries. The composites exhibited higher initial capacity and improved rate performance, attributed to the unique interlayer structure of graphene oxide and its functional groups.
Article
Chemistry, Organic
Nallappan Sundaravelu, Anuradha Nandy, Govindasamy Sekar
Summary: An efficient visible light-mediated photocatalyst-free C-S cross-coupling reaction has been developed for the synthesis of thiochromane derivatives through photoinduced electron transfer (PET). This methodology was further applied to the synthesis of thiochroman-4-ol via intermolecular three-component cross-coupling reaction. The reaction mechanism involves EDA complex formation, thioester cleavage, inter- or intramolecular sulfa-Michael addition, followed by aldol reaction sequence. The formation of EDA complex between aryl iodides and xanthate has been confirmed through spectroscopic experiments and DFT calculations.
Article
Chemistry, Multidisciplinary
Marco T. T. Passia, Niklas Bormann, Jas S. S. Ward, Kari Rissanen, Carsten Bolm
Summary: Despite being promising for applications in medicinal and agrochemical fields, sulfondiimines have been marginalized compounds. This study presents a metal-free synthetic method for the synthesis of N-monosubstituted sulfondiimines, overcoming their limitations in synthesis accessibility. By reacting S,S-dialkyl substrates with iodine, DBU, and iminoiodinanes in MeCN, the corresponding sulfondiimines were obtained with yields up to 85% (25 examples). Valuable free NH-N ' H-sulfondiimines were accessed through N-deprotection under mild reaction conditions. Experimental results and analysis propose a mechanistic pathway diverging from the radical-based iodine/iminoiodinane mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Environmental Sciences
Shiv Shankar, Lily Jaiswal, Jong-Whan Rhim
Summary: Interest in sulfur nanoparticles (SNPs) has grown due to their antibacterial and anticancer activity in food, agriculture, and biomedical fields, but concerns have been raised about potential risks to the environment and health. Recent research has focused on the effects of SNPs on plant and animal cells, with limited understanding of their mechanism of action on other microorganisms and human cells. This review aims to discuss the synthesis, properties, characterization, and biological applications of SNPs to enhance understanding of their applicability.
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
(2021)
Article
Chemistry, Applied
Shanping Chen, Kai Hu, Wei Feng, Guojiang Mao, Yuxia Li, Guo-Jun Deng
Summary: A direct strategy for the synthesis of fused thienoindoles from substituted indoles and elemental sulfur has been reported. This method yields a range of structurally valuable fused thienoindoles in 51-78% yield under transition-metal-free conditions, potentially useful in pharmaceutical industry and organic functional materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Thomas Q. Davies, Michael C. Willis
Summary: Sulfinylamines, known for their reactivity as sulfur electrophiles and in Diels-Alder reactions, have been underutilized in organic synthesis in recent decades. Recent research has shown their potential in one-pot syntheses of sulfoximines and sulfonimidamides, highlighting their different reactivity modes and unappreciated potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Polymer Science
Kun Woo Park, Elizabeth A. Tafili, Flora Fan, Zoran Zujovic, Erin M. Leitao
Summary: Inverse vulcanisation was used to stabilise polysulfide chains through cross-linking with cyclosiloxane cross-linkers. Two series of polysulfides were successfully synthesized, with different weight percentages of sulfur, using tetravinyl-tetramethyl-cyclotetrasiloxane (TVTSi) and pentavinyl-pentamethyl-cyclopentasiloxane (PVPSi) as the cross-linkers. The polysulfide materials exhibited swelling in non-polar solvents and showed potential for selective solvent absorption applications.
Article
Chemistry, Multidisciplinary
Pavol Ondrisek, Margaux Elie, Marion Pupier, Adiran Aguirre, Amalia Poblador-Bahamonde, Celine Besnard, Jerome Lacour
Summary: In this study, the issue of loss of emissive properties in cationic compounds caused by the electron-donating groups (EDGs) is successfully addressed by introducing acetylene derivatives. Interestingly, a general dynamic stereoisomerism phenomenon is observed for the compounds derived from achiral DAOTA cores, attributed to the influence of the geometry of the side chains.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Isabelle Gillaizeau, Ismael Dondasse, Cyril Nicolas, Liliane Mimoun, Volodymyr Sukach, Herve Meudal
Summary: An efficient method for the catalytic preparation of new beta-borylated enamides was achieved through regioselective iridium-catalyzed C(sp(2))-H borylation under relatively mild conditions. This method demonstrates broad substrate scope, good functional group tolerance, and efficient scale-up. The resulting C-3 borylated enamides can be advantageously utilized in cross-coupling reactions and rapidly converted into valuable 3,3-dihalogeno-2-methoxypiperidines.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Malte Oppermann, Francesco Zinna, Jerome Lacour, Majed Chergui
Summary: This study demonstrates trapping of the high-spin state in iron-based spin-crossover complexes by controlling the chiral configuration. The high-spin-state decay is found to be accompanied by changes in optical activity, reflecting coupling to a symmetry-breaking torsional mode. Diastereoselective ion pairing suppresses vibrational population and increases the high-spin-state lifetime. These findings motivate the synthetic control of torsional modes in iron(II) complexes to manipulate their spin-crossover dynamics as a complementary approach.
Article
Chemistry, Multidisciplinary
Yana Nikolova, Bibiana Fabri, Pau Moneva Lorente, Alejandro Guarnieri-Ibanez, Adiran de Aguirre, Yoshiki Soda, Gennaro Pescitelli, Francesco Zinna, Celine Besnard, Laure Guenee, Dimitri Moreau, Lorenzo Di Bari, Eric Bakker, Amalia Poblador-Bahamonde, Jerome Lacour
Summary: In this study, chiral quinacridines react multiple times with alpha-diazomalonates under Ru-II and Rh-II catalysis, achieving chemo and regioselective insertions of metal carbenes. This versatile method allows for the introduction of mono- or bis-functionalized malonate derivatives, which can be used to tune optical and chemical properties and for cellular bioimaging.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Lucas Frederic, Bibiana Fabri, Laure Guenee, Francesco Zinna, Lorenzo Di Bari, Jerome Lacour
Summary: In this study, tris(arene)-functionalized cationic [4]helicenes are synthesized with full regioselectivity and enantiospecificity using Ir- and Pd-catalysis in essentially one-pot, starting from a trivial precursor (17 examples). The poly-addition of aryl groups improves key optical properties, such as fluorescence quantum yields and lifetimes. Electronic circular dichroism and circularly polarized luminescence signatures are observed up to the far-red domain, particularly with additional arenes prone to aggregation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Optics
Jeremy R. Rouxel, Benedikt Roesner, Dmitry Karpov, Camila Bacellar, Giulia F. Mancini, Francesco Zinna, Dominik Kinschel, Oliviero Cannelli, Malte Oppermann, Cris Svetina, Ana Diaz, Jerome Lacour, Christian David, Majed Chergui
Summary: Chirality, a structural property of molecules, has significant implications in various fields. A new approach to probe molecular chirality using helical dichroism has been demonstrated on a disordered sample for the first time. By using hard X-rays with spiral Fresnel zone plates, researchers have successfully induced orbital angular momentum (OAM) and obtained helical dichroism spectra of a disordered powder sample, opening up new possibilities for studying the interaction between molecular chirality and OAM of light.
Article
Chemistry, Organic
Baptiste Taffoureau, Isabelle Gillaizeau, Pascal Retailleau, Cyril Nicolas
Summary: In this study, the synthesis and crystallization of 2,3,5-tri-O-benzyl-D-xylofuranose led to the isolation of the alpha anomer, with a small contamination of the beta form. The crystallographic structure of the alpha anomer was determined at 100 K and refined using a Hirshfeld atom refinement approach.
Article
Chemistry, Multidisciplinary
Ke-Feng Zhang, Nidal Saleh, Michal Swierczewski, Arnulf Rosspeintner, Francesco Zinna, Gennaro Pescitelli, Celine Besnard, Laure Guenee, Thomas Burgi, Jerome Lacour
Summary: A chiral bispyrene macrocycle was synthesized for intermolecular excimer fluorescence upon aggregation using a double hydrothiolation method followed by intramolecular oxidation. High stereoselectivity was achieved for the thiol-ene additions under templated conditions. The structural evolution upon aggregation was monitored by ECD/CPL.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Olivier Viudes, Alejandro Guarnieri-Ibanez, Celine Besnard, Jerome Lacour
Summary: By using electron-rich or electron-poor N-substituted oxazolidines as substrates, it is possible to selectively form either ammonium or oxonium ylides with the presence of ?-imino carbenes. Under dirhodium catalysis (2 mol%), treatment of 5-membered oxazolidine precursors with N-sulfonyl-1,2,3-triazoles allows for the regiodivergent synthesis of either 8-membered 1,3,6- or 1,4,6-oxadiazocines based on the initial N or O reactivity with the carbene.
Article
Chemistry, Multidisciplinary
David Pal, Celine Besnard, Adiran de Aguirre, Amalia I. Poblador-Bahamonde, Gennaro Pescitelli, Jerome Lacour
Summary: Hydrogen bonding plays a significant role in chemical reactions, conformation, and stereochemistry. This study introduces a novel dye, tetranitrofluorenone oximate, which can visually detect hydrogen-bond donating species and quickly determine the strength of hydrogen bonding by monitoring hypsochromic shifts. The molecule also exhibits atropisomeric conformations, and enantiopure bis-thioureas are found to be the most effective hydrogen bond donors for chiral induction, as demonstrated by electronic circular dichroism and time-dependent density functional theory calculations. Furthermore, bis-thioureas are used as chiral reagents in asymmetric 1,3-dipolar cycloadditions, with the electronic circular dichroism sensing of stereoinduction serving as an indirect method to select the most effective hydrogen bond donor for asymmetric synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Daniel Kamzol, Maxime Neuville, Chloe Cocaud, Killian Tiger, Baptiste Taffoureau, Krzysztof Lewinski, Justyna Jaszczyk, Olivier R. Martin, Sebastian Bas, Sylvain Routier, Isabelle Gillaizeau, Frederic Buron, Cyril Nicolas
Summary: This study comprehensively investigates the preparation and reactivity of N-tert-butanesulfinyl glycosylamines with simple Grignard and organo lithium reagents in batch and continuous flow chemistry. These carbohydrate derivatives, acting as latent imine equivalents, react readily with various carbon nucleophiles, making them useful precursors for the diastereoselective synthesis of bioactive compounds such as iminosugar-C-glycosides. Additionally, a hybrid protocol combining flow addition of benzylmagnesium chloride to a (S-R)-arabinofuranosylamine substrate at room temperature with a batch cyclization protocol is introduced for the first time. Notably, this semi-continuous flow process shortens the synthesis of imino-C-glycoside scaffolds to a single workday.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
M. Baljozovic, B. Arnoldi, S. Grass, J. Lacour, M. Aeschlimann, B. Stadtmueller, K. -H. Ernst
Summary: It has been shown that electrons interact differently with chiral molecules depending on their polarization. Previous photoemission experiments on enantiomeric pure monolayers of heptahelicene reported opposite asymmetries in spin polarization, attributed to the chirality-induced spin selectivity effect. However, these experiments lack the necessary angular and energy resolution to understand the mechanism of this phenomenon. To fill in the gaps, a detailed spin- and angle-resolved photoemission spectroscopy study of heptahelicene layers on a Cu(111) substrate was conducted, but no chirality-induced spin asymmetry in photoemission was observed. Possible reasons for the absence of spin-dependent electron transmission signatures through the chiral molecular layer are briefly discussed.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Pragya Verma, Christoph Nancoz, Johann Bosson, Geraldine M. Labrador, Jerome Lacour, Eric Vauthey
Summary: By combining ultrafast time-resolved fluorescence and transient electronic absorption, we investigated the stereoselectivity in the static stage of photoinduced electron transfer (ET). Our results show that the quenching dynamics for different diastereomeric pairs are the same, regardless of solvent polarity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexandre Homberg, Federica Navazio, Antoine Le Tellier, Francesco Zinna, Alexandre Fuerstenberg, Celine Besnard, Lorenzo Di Bari, Jerome Lacour
Summary: This research successfully synthesized a series of chiral amide-based bis-pyridine substituted polyether macrocycles through a simple two-step synthesis protocol, with one ligand showing efficient complexation with terbium(iii) ions, leading to interesting chiroptical properties observed in absorbance and fluorescence.
DALTON TRANSACTIONS
(2022)
Proceedings Paper
Materials Science, Multidisciplinary
Johann Bosson, Geraldine M. Labrador, Denis Jacquemin, Jerome Lacour
Summary: The intramolecular condensation of ortho substituents of triaryl carbenium ions can lead to the formation of cationic helicenes, which exhibit extended optical properties and intense chiroptical properties that can be tailored in the far red to near infra-red (NIR) spectral windows through orthogonal late-stage functionalization strategies. These molecules have potential applications in material sciences.
MATERIALS TODAY-PROCEEDINGS
(2022)