Article
Chemistry, Multidisciplinary
Mathis J. Benedikter, Janis V. Musso, Wolfgang Frey, Roman Schowner, Michael R. Buchmeiser
Summary: Despite their excellent selectivities and activities, Mo- and W-based catalysts for olefin metathesis have not been widely used due to their air sensitivity. The synthesized cationic-at-metal molybdenum and tungsten imido alkylidene NHC nitrile complexes are stable in air and can catalyze olefin metathesis reactions without prior activation. The presence of a nitrile ligand is crucial for their stability, while variations in imido and anionic ligands affect reactivities and stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Jennifer Morvan, Antonio Del Vecchio, Jakub Talcik, Dylan Bouetard, Marc Mauduit
Summary: Asymmetric Olefin Metathesis (AOM) is a highly versatile synthetic tool for producing chiral building blocks with excellent enantiopurity. Catalysts that can control both the Z-selectivity and enantioselectivity of metathesis transformations are in high demand due to the ubiquity of Z-alkene moiety in natural products. This review comprehensively covers all the breakthroughs achieved in the challenging field of Z-enantioselective olefin metathesis, which is important in the total synthesis of complex molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Augustin Nouaille, Jan Lorkowski, Xavier Pannecoucke, Marc Mauduit, Thomas Poisson, Samuel Couve-Bonnaire
Summary: This article presents a review of the challenges in using fluoroalkenes in ring-closing metathesis and cross-metathesis, highlighting the major developments in this field in recent years.
Article
Chemistry, Physical
Seongwook Park, Seunghwan Byun, Huijeoung Ryu, Hyungwoo Hahm, Junseong Lee, Sukwon Hong
Summary: Novel ruthenium catalysts bearing azobenzene groups were developed for olefin metathesis reactions, demonstrating an on-off switching ability in ring-closing metathesis reactions depending on UV irradiation. Various types of olefin metathesis reactions, such as ring-opening metathesis, cross-metathesis, and ethenolysis, exhibited photoswitching phenomena. The reversible feature of photoswitching was confirmed by observing the photoisomerization of azobenzene-bearing cyclic(alkyl)(amino)carbene ligands and the corresponding ruthenium catalysts using UV-vis spectroscopy.
Article
Chemistry, Multidisciplinary
Carla Casadevall, Vlad Martin-Diaconescu, Wesley R. Browne, Sergio Fernandez, Federico Franco, Noemi Cabello, Jordi Benet-Buchholz, Benedikt Lassalle-Kaiser, Julio Lloret-Fillol
Summary: In this study, a Ru(IV) side-on peroxo complex is reported as a 'missing link' for species formed after the rate-determining O-O bond-forming step, confirming water nucleophilic attack as a viable mechanism for O-O bond formation.
Review
Chemistry, Multidisciplinary
Atitegeb Abera Tsedalu
Summary: Olefin metathesis is a metal-mediated C-C bond exchange reaction that is widely used in the synthesis of organic compounds, polymers, drugs, plastics, and other synthetic materials. It involves breaking the double bond of an olefin precursor to redistribute the fragments and obtain new products.
JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Applied
Ravindra S. Phatake, Noy B. Nechmad, Ofer Reany, N. Gabriel Lemcoff
Summary: A selective ring-closing metathesis (RCM) reaction using latent sulfur chelated ruthenium iodide benzylidenes as catalysts, activated by thermal and photochemical stimuli, has been reported. This method enables the formation of large macrocycles with high yields, especially for dienes with one terminal alkene and one internal double bond. For substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Louis Monsigny, Anna Kajetanowicz, Karol Grela
Summary: This review discusses a distinct class of ruthenium olefin metathesis catalysts with unsymmetrical N-heterocyclic carbene (uNHC) ligands, highlighting their advantages such as thermodynamic stability, chemical latency, selectivity, and compatibility with green solvents in specialized metathesis transformations. Despite being niche, uNHC complexes have the potential to be implemented in various industrial processes like valorization of Fischer-Tropsch olefin fractions, ethenolysis of renewable products, and modern pharmaceutical production.
Article
Multidisciplinary Sciences
Agata Tyszka-Gumkowska, Vishal B. Purohit, Tomasz Nienaltowski, Michal Dabrowski, Anna Kajetanowicz, Karol Grela
Summary: In this study, diverse polyfunctional substrates were subjected to olefin metathesis reactions in water emulsions using hydrophobic ruthenium catalysts. Instead of using surfactants, ultrasound and microwave techniques were tested on a small scale while conventional heating and mechanical stirring were effective on a larger scale. The developed conditions allowed for low catalyst loadings and simple isolation and purification of the products. The synthetic protocol was successfully applied in the large-scale synthesis of a pharmaceutically related product, sil-denafil (Viagra) derivative.
Article
Chemistry, Physical
Haoyu Wang, Haitao Yu, Dong Bai, Dan Yao, Yongjun Han, Yichao Shi, Zhiqun Wang
Summary: A ruthenium olefin metathesis catalyst (C1-H) with a novel NHC ligand tethered by an ethoxy-pyridyl arm was synthesized and compared with its methylated derivative (C1-Me). The study showed profound variations in initiation rate, kinetics, metathesis activity, and decomposition behavior between these two catalysts. The remote torsional strain was found to have a considerable influence on the catalytic activity and decomposition behavior of this ligand class.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Leonildo A. Ferreira, Josiane T. Silva, Raissa G. Alves, Kelley C. B. Oliveira, Eduardo N. dos Santos
Summary: In this study, the cross metathesis of estragole and methyl sorbate was investigated to produce methyl 6-(4-methoxyphenyl)hexa-2,4-dienoate with good conversion and selectivity using ruthenium-based metathesis catalysts at low catalyst loadings as 50 ppm (0.005 mol%) and minimal solvent. This demonstrates the importance of catalyst selection and reaction conditions in achieving the desired product conversion and selectivity.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Applied
Eva Pump, Albert Poater, Naeimeh Bahri-Laleh, Raffaele Credendino, Luigi Serra, Vittorio Scarano, Luigi Cavallo
Summary: This study computationally investigates the origin of chemo-, regio- and stereoselectivity in cross metathesis reactions leading to the desired product. By comparing the relative stabilities of intermediates and products, as well as transition states, the probability for each pathway is linked. The transition states in each reaction play a crucial role in tuning the regio- and stereoselectivity by defining the energy barriers needed to form the final product. The research findings provide valuable insights for understanding the selectivity in new olefin metathesis reactions and a web-server is developed to support future predictive catalysis.
Article
Chemistry, Physical
Antonio Del Vecchio, Jakub Talcik, Sophie Colombel-Rouen, Jan Lorkowski, Melinda R. Serrato, Thierry Roisnel, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: New Blechert-type ruthenium complexes with cyclic(alkyl)(amino)carbene (CAAC) ligands show remarkable thermal stability in solution and excellent catalytic performances in various metathesis reactions. They exhibit high catalytic activity at low loading and can achieve high enantiomeric excess in asymmetric metathesis reactions.
Article
Chemistry, Physical
David Skoda, Ran Zhu, Barbora Hanulikova, Ales Styskalik, Vit Vykoukal, Petr Machac, Lucie Simonikova, Ivo Kuritka, Claude Poleunis, Damien P. Debecker, Yuriy Roman-Leshkov
Summary: In this study, we demonstrate that amorphous and porous molybdenum silicate microspheres are highly active catalysts for heterogeneous propylene metathesis. These microspheres were synthesized via a nonaqueous condensation method and showed significantly higher catalytic activity compared to conventional silica-supported catalysts.
Article
Chemistry, Inorganic & Nuclear
Zuzhang Lin, Zhewei Yan, Yapeng Cai, Jian Xuan, Nanxiang He, Hong Zhang
Summary: Enyne metathesis reactions involving metallacyclobutene intermediates have been extensively studied and utilized in various synthetic processes and catalytic transformations. In this study, we investigated the utilization of metalla-aromatic in classical [2 + 2] cycloaddition, where eta(3)-allyl structures were formed stoichiometrically through hydrogen-bonding-induced [2 + 2] cycloaddition between propynol and a ruthenabenzene complex. The impact of intramolecular hydrogen bonding interaction was analyzed using experimental and computational studies.
Article
Chemistry, Multidisciplinary
Seoneun Jeong, Lianjin Zhang, Jaewook Kim, Jintaek Gong, Jonghoon Choi, Kang Min Ok, Yunho Lee, Sunbum Kwon, Hee-Seung Lee
Summary: This study presents the first metal-coordination-mediated assembly of beta-peptide foldamers with 12-helical folding propensity, resulting in unique entangled metal-peptide frameworks. The formation of network structures is accompanied by notable conformational distortions of the foldamer ligands. This work is expected to be an important benchmark for further structural evolution and mechanistic investigation in the field of metal-peptide frameworks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Taehyung Kim, Se Hun Joo, Jintaek Gong, Sungho Choi, Ju Hong Min, Yongchul Kim, Geunsik Lee, Eunji Lee, Soojin Park, Sang Kyu Kwak, Hee-Seung Lee, Byeong-Su Kim
Summary: In this study, highly crystalline PICs with various pore dimensions were successfully synthesized under geomimetic hydrothermal conditions. The solubility of the oligomeric intermediates under hydrothermal conditions was found to affect the stacking structures of the crystalline PICs. Additionally, the synthesized PICs show promising potential as an anode material in lithium-ion batteries due to their unique redox-active properties and high surface area.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Rokam Jeong, Jae-Hoon Eom, Jintaek Gong, Minsang Kang, Jaewook Kim, Hee-Seung Lee
Summary: This study reports the first example of programmed radial assembly of anisotropic microparticles derived from a helical foldamer with a C-terminal cysteine residue. Surface-exposed thiols play a crucial role in facilitating interparticle hydrogen bonding to form higher-order structures in an aqueous solution.
Review
Chemistry, Multidisciplinary
Byeonghoon Choi, Dongwoo Shin, Hee-Seung Lee, Hyunjoon Song
Summary: Metal oxide semiconductors are suitable for chemiresistive gas sensors, with p-type oxide semiconductors being improved through nanostructuring and forming p-n heterojunctions for enhanced sensitivity at low temperatures. These materials are gaining attention as advanced gas sensing materials for environmental and healthcare monitoring, especially when combined with strategies like light activation and sensor arrays for exclusive gas detection at ultra-low concentrations.
Article
Chemistry, Multidisciplinary
Chang-Hee Whang, Jungwoo Hong, Dohyeon Kim, Hong Ryu, Wonsik Jung, Youngju Son, Hyeongseop Keum, Jinjoo Kim, Hocheol Shin, Eugene Moon, Ilkoo Noh, Hee-Seung Lee, Sangyong Jon
Summary: This study reports a library of glycocalyx-mimicking nanoparticles for screening and identification of cancer-targeting nanomedicines. The researchers found that certain nanoparticles selectively targeted different tumors and exhibited potent therapeutic effects. The results suggest that this nanoparticle library has a versatile application potential beyond cancer treatment.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Physical
Marjorie Ladd-Parada, Katrin Amann-Winkel, Kyung Hwan Kim, Alexander Spah, Fivos Perakis, Harshad Pathak, Cheolhee Yang, Daniel Mariedahl, Tobias Eklund, Thomas J. Lane, Seonju You, Sangmin Jeong, Matthew Weston, Jae Hyuk Lee, Intae Eom, Minseok Kim, Jaeku Park, Sae Hwan Chun, Anders Nilsson
Summary: Using time-resolved wide-angle X-ray scattering, this study investigated the early stages of crystallization of supercooled water. It was found that the crystallizing phase is stacking disordered ice, with a small portion of hexagonal ice also observed. The final crystalline fraction in low-density amorphous ice was considerably lower than that in high-density amorphous ice.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Organic
Thomas T. Kim, Chungwoo Lee, Dongwook Kim, Hee-Seung Lee, Sunkyu Han
Summary: In this paper, we present the synthesis and reactivity of 1-hydroxyherquline A, and discuss the challenges encountered during its conversion to herquline A. These findings provide valuable insights for future research and synthesis of herquline A.
Review
Biochemistry & Molecular Biology
Seoneun Jeong, Kwonjung Lee, Sung Hyun Yoo, Hee-Seung Lee, Sunbum Kwon
Summary: Metal-peptide networks are structures assembled from short peptides and metal ions, known for their unique and complicated features. However, limitations such as designability, stability, and modifiability have hindered their practical applications. This review summarizes important milestones in the development of crystalline metal-peptide networks and analyzes their structural features and potential applications, providing insights for the development of new metal-peptide networks with more sophisticated structures and novel functions.
Article
Chemistry, Multidisciplinary
Sung Hyun Yoo, Jintaek Gong, Lianjin Zhang, Seoneun Jeong, Jin Kim, Hee-Seung Lee
Summary: This study reported transition metal complexes from an unnatural beta-amino acid, showing different coordination modes and structural features.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Dohyun Yoo, Chang-Hee Whang, Jungwoo Hong, Dohyeon Kim, Monica Celine Prayogo, Youngju Son, Wonsik Jung, Seojung Lee, Hee-Seung Lee, Sangyong Jon
Summary: Current medications for inflammatory bowel disease (IBD) have limited effectiveness and severe side effects. Therefore, there is an urgent need for novel therapeutic approaches that can specifically target inflamed areas in the gastrointestinal tract with minimal systemic effects. In this study, researchers constructed a library of anti-inflammatory nanoparticles called GlyNPs and evaluated their therapeutic potential in a mouse model of IBD. By attaching bilirubin (BR) to a library of glycopolymers, the researchers identified a candidate GlyNP capable of targeting macrophages in the inflamed colon and effectively alleviating colitis symptoms. These findings suggest that the BR-attached GlyNP library can serve as a platform for identifying anti-inflammatory nanomedicines for various inflammatory diseases.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Danim Lim, Wonchul Lee, Jungwoo Hong, Jintaek Gong, Jonghoon Choi, Jaewook Kim, Seolhee Lim, Sung Hyun Yoo, Yunho Lee, Hee-Seung Lee
Summary: We introduce a novel cyclic β-amino acid, trans-(3S,4R)-4-aminotetrahydrothiophene-3-carboxylic acid (ATTC), as a versatile building block for designing peptide foldamers with controlled secondary structures. Our findings reveal that ATTC-containing foldamers can adopt 12-helical conformations similar to their isosteres and offer the possibility of fine-tuning their properties via post-synthetic modifications. In particular, chemoselective conjugation strategies demonstrate that ATTC provides unique post-synthetic modification opportunities, which expand their potential applications across diverse research areas.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jaewook Kim, Jungwoo Hong, Mi Jeong Park, Hee-Seung Lee
Summary: This groundbreaking research uncovers an approach for crafting chiral channels in metal-peptide networks (MPNs). The strategic integration of foldamer ligands and CuI clusters allows precise, atomic-level modifications. The technique expedites enantiomer discrimination in mixtures and prompts adaptable molecules to adopt specific chiral forms. It promises the potential for multifunctional materials useful in catalysis, drug delivery, and sensing technologies.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Jungwoo Hong, Wonchul Lee, Hee-Seung Lee
Summary: This article presents an optimized method for the stereoselective synthesis of five-membered alicyclic and heterocyclic trans-beta-amino acid derivatives, which allows for high yields and scalable production of the desired building blocks.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Sangmin Jeong, Eunji Park, Joonghan Kim, Kyung Hwan Kim
Summary: By conducting nonadiabatic molecular dynamics simulations, we investigated the photoisomerization dynamics of 1,2-dihydro-1,2-azaborine and identified three different reaction pathways. Our results confirmed that the photoisomerization of azaborine follows the energetically favored pathway, predominantly forming the Dewar isomer, which is consistent with experimental observations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Jihye Park, Hee-Seung Lee, Hyungjun Kim, Jeong-Mo Choi
Summary: In this study, we assessed the performance of three popular force fields in predicting the conformational propensities of a beta-peptide foldamer. Our results showed the unanimous role of hydrogen bonds in shaping energy landscapes. These findings contribute to the improvement of force fields and understanding the role of solvents in peptide folding, crystallization, and engineering.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
