Review
Chemistry, Multidisciplinary
Muneshwar Nandeshwar, Suman Mandal, Subramaniam Kuppuswamy, Ganesan Prabusankar
Summary: Sustainable noble metal-N-heterocyclic carbenes (NHC's) have gained significant attention in both the chemical industry and academic community due to environmental concerns and resource scarcity. The choice of catalyst supports plays a crucial role in heterogeneous catalysis, with graphene oxide (GO)/reduced graphene oxide (rGO) support showing great potential due to their larger surface area, inertness towards chemical transformations, and easy surface functionalization. Marrying metal-N-heterocyclic carbenes with GO/rGO support offers novel heterogeneous complexes with improved catalytic efficiency without sacrificing product selectivity, presenting opportunities for the chemical and pharmaceutical industry. However, limited examples of this approach are reported in the literature, highlighting the need for comprehensive reviews on metal-NHC synthesis on GO/rGO support and synthetic strategies for grafting M-NHC onto GO/rGO surface, as well as understanding the catalytic efficiency and mechanisms of non-covalent grafting methodology to design engineered catalysts for unexplored catalytic applications.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Wan-Qiang Wang, Zhi-Qin Wang, Wei Sang, Rui Zhang, Hua Cheng, Cheng Chen, Da-Yong Peng
Summary: This study investigates the factors influencing product distribution in the metal-catalyzed dehydrogenative coupling of alcohols and amines to access amides using N-heterocyclic carbene-based Ru (NHC/Ru) complexes. The experimental results show that Ru loadings, added NHC precursors, and the electronic/steric properties of ancillary NHC ligands have a significant impact on the selectivity and yield of the catalytic process.
Article
Chemistry, Multidisciplinary
Yu-Yang Zhou, Yang-Ming Ding, Wei Zhao, Jian-Hua Dong, Liang-Zhi Li, Hong-Yuan Chen, Jing-Juan Xu
Summary: Three new ruthenium(ii) complexes with N-heterocyclic carbene ligands have been synthesized and shown to be efficient near-infrared ECL luminophores. These complexes demonstrate higher or comparable ECL efficiency compared to traditional Ru(bpy)(3)(2+), indicating great potential for future applications in NIR ECL imaging.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Zikun Wang, Nikolaos V. Tzouras, Steven P. Nolan, Xihe Bi
Summary: Silver N-heterocyclic carbenes (Ag-NHCs) have good biocompatibility and are widely used in medicine and coordination chemistry, but their coordination with silver can weaken the Lewis acidity of Ag(I), resulting in slow development as catalysts. Future opportunities lie in further research on the catalytic mechanisms of Ag-NHCs to enhance their catalytic activity.
TRENDS IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kseniya V. Arsenyeva, Kira I. Pashanova, Olesya Yu. Trofimova, Irina V. Ershova, Maxim G. Chegerev, Alyona A. Starikova, Anton V. Cherkasov, Mikhail A. Syroeshkin, Anna Ya. Kozmenkova, Alexandr V. Piskunov
Summary: The newly synthesized monomeric O,N-heterocyclic germylene (Ad)APGe (1) shows weak interactions between molecules in the crystal and exhibits excellent redox activity and catalytic properties.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Applied
Wenli Bai, Jian Sun, Dongyang Wang, Sheng-Di Bai, Liang Deng
Summary: This study investigates the catalytic performance of low-coordinate cobalt(0) N-heterocyclic carbene (NHC) complexes in the hydrosilylation reaction of alkynes, revealing the fine selectivity mechanism governed by the steric nature of the NHC ligand.
APPLIED ORGANOMETALLIC CHEMISTRY
(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
Chemistry, Applied
Zeynep Tunali, Sidal Dagistanli, Sevval Kubalas, Bengi Ozgun Ozturk
Summary: The tablet-based catalytic systems offer improved stability, ease of handling, and dosage delivery of transition metal catalysts for organic transformation reactions. However, the traditional paraffin wax-based tablet catalysts cannot be recycled due to their solubility in common organic solvents. This study developed recyclable tablet catalyst systems based on poly(dimethylsiloxane) (PDMS) containing gold(I) N-heterocyclic carbene complexes for alkyne hydration reactions in aqueous medium. The tablet catalysts showed high performance and can be easily isolated from the reaction media in solid phase.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Multidisciplinary
Perrin Godbold, Grayson Johnson, Akachukwu D. Obi, Rebecca Brown, Sooyeon Hwang, Robert J. Gilliard, Sen Zhang
Summary: The removal of surfactants from colloidal synthesized nanocrystals via ligand exchange with N-heterocyclic carbenes (NHCs) followed by protonation of the NHC ligands in acid efficiently cleans the nanocrystals' surface while preserving their uniform morphology and structure for catalysis. This surface activation strategy showed significantly improved catalytic activities for monodisperse Pt, Pd, and Au nanocrystals, surpassing other cleaning methods, as demonstrated in glycerol oxidation and CO2 reduction electrochemical reactions. This work highlights a new surface activation strategy that enables the efficient use of well-defined nanocrystal libraries for catalysis and other applications prepared by colloidal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This review article aims to highlight recent advances in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. The synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs) based on a 1,3-imidazole framework are also presented. iMICs and ADCs have the potential to push the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligand sets, and more.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
David P. Tilly, William Cullen, Heng Zhong, Romain Jamagne, Inigo Vitorica-Yrezabal, Simon J. Webb
Summary: By investigating the effect of remotely induced changes in ligand folding, a potential pathway towards remote conformational control of organometallic catalysts has been discovered. The study on dynamic folding of Aib peptides revealed that the chiral conformational preference of N-terminal residues can be relayed to the axially chiral Rh(NHC) complex in the helical body.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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
Peibo Chen, Tingkai Xiong, Yingming Pan, Ying Liang
Summary: This review focuses on the application of N-heterocyclic carbene and related complexes in the chemical fixation of carbon dioxide. Various technologies, including carbene-metal catalytic system, carbene-free-metal catalytic system, and synergistic catalytic technology, are discussed. The possible role of carbene materials in chemical carbon fixation is explored by analyzing typical mechanisms.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hang Shen, Michael B. Larsen, Allison G. Roessler, Paul M. Zimmerman, Andrew J. Boydston
Summary: A new flex-activated mechanophore has been discovered, which releases an N-heterocyclic carbene (NHC) under mechanical load. This design demonstrates a promising first step towards flex-activated designs with downstream reactivities, allowing for iterative activation increases in the material through non-destructive compression cycles. The potential modularity of the mechanophore design is highlighted by the demonstration of two different NHC structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Anna C. Closs, Maximilian Bechtel, Oliver Trapp
Summary: Evolutionary biological processes lead to changes in heritable traits, where the responsible genetic information in DNA is altered, selected, and inherited through the mutation of the base sequence. Evolutionary changes at the molecular level of small organic molecules are unknown but represent an important prerequisite for the emergence of life, where catalysts can exhibit different selectivity during formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Editorial Material
Chemistry, Medicinal
Eiji Yashima, Katsuhiro Maeda, Oliver Trapp, Nina Berova, Simona Collina, Gennaro Pescitelli
Article
Chemistry, Physical
Sabrina Kraeh, Iris Kachel, Oliver Trapp
Summary: Palladium-catalyzed cross-coupling reactions are efficient methods for organic synthesis, but heteroatom-containing compounds often complicate these reactions. This study introduces a highly active phosphine ligand that enables excellent yields in C-N coupling reactions at ambient temperature. The unique structure of the ligand, incorporating a silicon atom and a cyclohexane moiety, results in electron-rich properties. This ligand facilitates a broad range of coupling reactions under mild conditions in palladium catalysis.
Article
Chemistry, Organic
Jan-Michael Menke, Oliver Trapp
Summary: For the preparation of chiral drugs, the combination of stereochemically stable and flexible catalysts with chiral auxiliaries is crucial. In this study, a successful approach to the spontaneous deracemization of tropos ligands for asymmetric catalysis was demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Editorial Material
Biochemistry & Molecular Biology
Oliver Trapp
Article
Biology
Laura Huber, Oliver Trapp
Summary: This study developed a method to investigate the reaction kinetics of single molecules in order to understand chiral symmetry breaking at the molecular level. The results showed that interlocking processes can amplify the occurrence of symmetry breaking, providing a promising direction for experimental implementation and identification of these processes.
ORIGINS OF LIFE AND EVOLUTION OF BIOSPHERES
(2022)
Article
Multidisciplinary Sciences
Guiyang Yao, Simone Kosol, Marius T. Wenz, Elisabeth Irran, Bettina G. Keller, Oliver Trapp, Roderich D. Suessmuth
Summary: This article reports the use of the term "ansamer" to describe the isomers of the bicyclic octapeptide alpha-Amanitin. The researchers synthesized analogs of alpha-Amanitin and analyzed their isomers, proposing and describing the term "ansamer" for these isomers.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Constanze Sydow, Christiane Seiband, Alexander F. Siegle, Oliver Trapp
Summary: Organophosphates play important roles in living organisms, but their prebiotic origins are unknown. In this study, the authors demonstrate the efficient formation of organophosphates through a phosphorylation reaction in liquid sulfur dioxide at room temperature. This reaction could have occurred in volcanic environments on Early Earth, and it also has potential applications in synthetic chemistry.
COMMUNICATIONS CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Lena C. Mayer, Simone Heitsch, Oliver Trapp
Summary: Asymmetric synthesis plays a crucial role in preparing enantiomerically pure compounds and controlling individual stereocenters in complex compound synthesis. It relies on the use of enantiopure catalysts and configurationally flexible ligands or organocatalysts. The design of smart catalyst systems that combine supramolecular recognition, stereoconvergent alignment, and catalysis has been successful in enhancing enantioselectivity in asymmetric catalysis.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Editorial Material
Chemistry, Medicinal
Simona Collina, Simone Lucarini, Jordi Benet-Buchholz, Simona Collina, Oliver Trapp, Gennaro Pescitelli, Nina Berova
Article
Chemistry, Medicinal
Simone Heitsch, Lena Carina Mayer, Yanis Luca Pignot, Oliver Trapp
Summary: Soai's asymmetric autocatalysis is a remarkable example of symmetry breaking and enantioselective amplification in the alkylation of pyrimidine-5-carbaldehydes. Zinc hemiacetalate complexes formed from the aldehydes and the chiral product alcohol were identified as highly active catalysts in this transformation. By studying the synthesis of coumarin homolog biaryl systems, it was found that they can form hemiacetals through intramolecular cyclization, with the ability to enable or disable this process depending on the tropos or atropos configuration.
Article
Chemistry, Multidisciplinary
Constanze Sydow, Fabian Sauer, Alexander F. Siegle, Oliver Trapp
Summary: Peptides play essential roles in the structure and catalytic functions of living organisms. The formation of peptides faces thermodynamic and kinetic barriers. Recent studies have explored various formation scenarios during the origin of life, including iron(III)-catalyzed condensations. However, iron(III)-catalysts often have low catalytic activity at elevated temperatures. This study demonstrates that reduced iron activated by acetic acid efficiently mediates peptide formation, providing a potential pathway for the formation of the first peptides in anoxic environments.
Review
Chemistry, Multidisciplinary
Lena C. Mayer, Simone Heitsch, Oliver Trapp
Summary: Asymmetric synthesis is a crucial technique for the preparation of chiral compounds and the control of stereocenters in complex syntheses. Configurationally flexible ligands and catalysts can be enriched through dynamic processes, leading to improved enantioselectivity in asymmetric catalysis. This strategy has significant implications for the development of new catalytic applications and understanding of chirality amplification and homochirality in biological systems.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Maximilian Bechtel, Eva Hummer, Oliver Trapp
Summary: Nucleotides play a vital role in organisms, but there has been no effective selective pathway for their formation. In this study, we have discovered a selective nucleotide synthesis reaction pathway under extremely mild prebiotic conditions for all major bases. This finding opens up new avenues for studying the origins of life.
Article
Chemistry, Multidisciplinary
Mario Grosch, Martin T. Stiebritz, Robert Bolney, Mario Winkler, Eric Jueckstock, Hannah Busch, Sophia Peters, Alexander F. Siegle, Joris van Slageren, Markus Ribbe, Yilin Hu, Oliver Trapp, Christian Robl, Wolfgang Weigand
Summary: This study provides evidence for mackinawite-supported reduction of KCN and proposes a reaction mechanism. The findings open new avenues for investigating other substrates for mackinawite-supported reactions and shed light on the relevance of this type of reaction to the origin of life on Earth.
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
