Article
Chemistry, Multidisciplinary
Samuel Pearce, Juan Perez-Mercader
Summary: By integrating various chemical processes, simplification of PISA process and routes to complexity and adaptation in chemical systems can be achieved.
ACS CENTRAL SCIENCE
(2021)
Review
Chemistry, Physical
Chang-Qing Qin, Cheng Zhao, Guo-Shu Chen, Yun-Lin Liu
Summary: Catalytic enantioselective azide-alkyne cycloaddition (E-AAC) is an efficient technology for constructing diverse chiral triazoles, with applications in synthetic and medicinal chemistry, biological chemistry, and materials science. Significant developments have been made in copper-, nickel-, iridium-, and rhodium-catalyzed E-AAC reactions in the past six years. This review summarizes these advancements according to different strategies implemented.
Review
Chemistry, Organic
Dileep Kumar Singh
Summary: Among the various approaches in organic synthesis, the click chemistry protocol, also known as CuAAC reaction, is commonly used to connect different moieties in a single framework. This review focuses on the synthesis and photophysical studies of porphyrin conjugates with meso-substituted and 1,2,3-triazole-fused structures. The triazole ring serves as a spacer and an electron transfer bridge between the attached chromophores and the porphyrin.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Suguru Yoshida, Yuki Sakata, Yoshihiro Misawa, Takamoto Morita, Tomoko Kuribara, Harumi Ito, Yuka Koike, Isao Kii, Takamitsu Hosoya
Summary: Efficient consecutive formation of 1,2,3-triazoles using multiazide platforms has been achieved in this study. A four-step synthesis of tetrakis(triazoles) was successfully performed from a tetraazide platform molecule, based on the unique clickability of the 1-adamantyl azido group. This method was applied to the convergent synthesis of tetrafunctionalized probes in a modular synthetic manner.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fan Yu, Zhaoman Zhou, Jiajia Song, Yanying Zhao
Summary: This study rationalized the mechanism of Cu(I)-catalyzed 5-enamine-functionalized fully substituted 1,2,3-triazole synthesis using density functional theory (DFT) and multicomponent artificial force-induced reaction (MC-AFIR) methods. The research provided important mechanistic insights for the interrupted CuAAC reaction and identified the rate-determining step as the transmetalation process along the triplet state potential energy surface. Further predictions suggest the role of solvent and extra strong ligand coordination in competitive reactions.
Article
Electrochemistry
Kun Liu, Kennedy S. Chen, Dipankar Sen, Hua-Zhong Yu
Summary: The newly selected DNAzyme CLICK-17 offers a sensitive and specific detection method for copper without the need for unstable reducing agents, providing rapid detection and no background signals.
ELECTROCHIMICA ACTA
(2021)
Review
Chemistry, Physical
Parveen Saini, Sonika, Gurjaspreet Singh, Gurpreet Kaur, Jandeep Singh, Harminder Singh
Summary: The Cu(I) catalyzed azide-alkyne cycloaddition using the "Click Reaction" is a highly stereoselective synthetic method for generating a library of organic molecules with diverse applications. Versatile Cu(I) complexes with tailoring capabilities can act as catalysts for forming 1,4-disubstituted products by stitching organic azide to alkyne.
MOLECULAR CATALYSIS
(2021)
Article
Materials Science, Multidisciplinary
Kseniya A. Bezlepkina, Sofia N. Ardabevskaia, Kseniia S. Klokova, Aleksei I. Ryzhkov, Dmitry A. Migulin, Fedor V. Drozdov, Georgij V. Cherkaev, Aziz M. Muzafarov, Sergey A. Milenin
Summary: Despite the presence of many methods for the preparation, functionalization, and vulcanization of polysiloxanes, the development of materials based on silicones still requires the introduction of new approaches that combine modern strategies such as atom-economical reactions and green chemistry principles. This work presents modern approaches to prepare linear and branched polyorganosiloxanes with azidopropyl functions at the silicon atom. The study demonstrates effective methods for introducing these groups and the possibility of postpolymerization functionalization under green conditions using click chemistry.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Mairead E. Bartlett, Scott A. Shuler, Daniel J. Rose, Lindsey M. Gilbert, Rachel A. Hegab, Thomas J. Lawton, Reid E. Messersmith
Summary: The study presents a novel approach to rapidly applying bioactive coatings on surfaces while maintaining protein bioactivity. By conjugating proteins into an adhesive network using an oPA-based linker, a higher retention rate of proteins on the surface was achieved, allowing for the creation of new functional materials with properties typically found in the biological domains.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Shivani Bhagat, Shilpa Dani, Ankit Verma, Ravinder Dharavath, Umesh R. Pratap
Summary: Covalent triazine frameworks (CTFs) are synthesized and integrated with copper ions to form a catalyst (Cu@CTF) with excellent performance for click reaction. The catalyst shows fast reaction rate, high yield, and recyclability, indicating its superior applicability in catalysis. This research advances the development and usage of functional CTF materials for catalysis.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Review
Biotechnology & Applied Microbiology
Priyank Purohit, Akanksha Bhatt, Ravi K. Mittal, Magda H. Abdellattif, Thoraya A. Farghaly
Summary: Polymer grafting is a technique to improve the morphology and properties of polymers. By creating copolymers or grafting, the physicochemical properties of polymers can be further modified. This review discusses various chemical approaches for polymer grafting, such as free radical reactions, click reactions, amide formation, and alkylation. The review also covers the importance of the graft-to approaches and their application in different fields.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2023)
Article
Biology
Z. Soederlund, A. Ibanez-Fonseca, S. Hajizadeh, J. C. Rodriguez-Cabello, J. Liu, L. Ye, E. Tykesson, L. Elowsson, G. Westergren-Thorsson
Summary: The study demonstrates the application of synthetic glycosaminoglycans in inducing desired cellular responses and the possibility of specific growth factor release using a modular 3D scaffold in vitro and in vivo.
COMMUNICATIONS BIOLOGY
(2022)
Article
Chemistry, Organic
T. Moritz Weber, Joerg Pietruszka
Summary: Copper-catalyzed alkyne azide click chemistry (CuAAC) is important for drug development and biological materials labeling. A new tridentate Cu-ligand called TDETA was synthesized as a scalable and non-toxic alternative to HN3 and the previously used DTEA ligand. TDETA showed excellent solubility in organic solvents and aqueous solutions, outcompeted commercial ligands THPTA and TBTA for various azide and alkyne combinations using Cu(I) and Cu(II) species, and had a 80% recovery yield.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Borja Cirera, Alexander Riss, Pingo Mutombo, Jose Urgel, Jose Santos, Marco Di Giovannantonio, Roland Widmer, Samuel Stolz, Qiang Sun, Max Bommert, Roman Fasel, Pavel Jelinek, Willi Auwarter, Nazario Martin, David Ecija
Summary: The design of organometallic complexes is crucial in modern organic chemistry and catalysis. On-surface synthesis has recently emerged as a disruptive method to design compounds and nanomaterials previously considered impossible. The activation of inner diacetylene moieties of a molecular precursor by copper surface adatoms has led to the formation of unprecedented organocopper metallacycles on Cu(111), paving the way for new avenues in organometallic compound engineering and polyyne chemistry on surfaces.
Article
Chemistry, Applied
Shaik Syed Hussain, Kesavarao Sykam, Ramanuj Narayan, Pratyay Basak
Summary: Si-PUTs were prepared by azide-alkyne cycloaddition, showing excellent surface hydrophobicity and anti-corrosion properties. A simple modification of aminopropyl trimethoxy silane produced a dialkyne terminated monomer, while azide-terminated urethane monomers were synthesized using azidoethanol and common diisocyanates. The successful formation of Si-PUTs was confirmed by FTIR and XPS analysis, and their performance as corrosion resistive coatings was evaluated comprehensively.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Chemistry, Organic
Tobias Babl, Oliver Reiser
Summary: The first enantioselective synthesis of (S)-meptazinol in 14 steps from a commercially available compound and the formal synthesis of two anti-Alzheimer's agents are reported. A novel ring expansion reaction provides an effective entry to 3,3-disubstituted azepanes that represent the core for a variety of approved drugs.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Manoj Kumar, Shalini Verma, Vivek Mishra, Oliver Reiser, Akhilesh K. Verma
Summary: The copper-catalyzed reactions under visible light irradiation have been successfully applied in the synthesis of aminated cyclopentene and cyclopentane derivatives. The method is compatible with various functionalities and demonstrates simplicity and affordability.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Woraluk Mansawat, Phanomsak Yukhet, Worawan Bhanthumnavin, Oliver Reiser, Tirayut Vilaivan
Summary: The use of C-2-symmetrical chiral amino alcohol ligands in combination with CuCl2 has been shown to be effective for the asymmetric acylation of dI-hydrobenzoins, with up to 99% ee obtained for the monoacylated products.
Article
Chemistry, Multidisciplinary
Alexander Reichle, Magdalena Koch, Hannes Sterzel, Lea-Joy Grosskopf, Johannes Floss, Julia Rehbein, Oliver Reiser
Summary: The visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents is reported. This method offers high yields, fast reaction times, and environmentally benign reaction conditions with a wide scope, allowing rapid functionalization of activated and unactivated olefins. Additionally, it demonstrates the late-stage functionalization of biologically active molecules and the upscaling to gram quantities, providing possibilities for further transformations such as the preparation of nitro- and aminocyclopropanes. Moreover, this study highlights the unique role of copper in photoredox catalysis by stabilizing and interacting with radical intermediates in its coordination sphere, as revealed by EPR studies that show its superior performance compared to iridium-based photocatalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nejc Petek, Helena Brodnik, Oliver Reiser, Bogdan Stefane
Summary: A Cu(I)-photoredox-catalyzed trifluoromethylchlorosulfonylation reaction of terminal alkynes under visible light conditions has been developed. The reaction yields trifluoromethyl-substituted vinylsulfonyl chlorides, which can subsequently be coupled to a second alkyne under photocatalytic conditions. The method shows high regio- and stereoselectivity and can be applied to aliphatic and aromatic alkynes with various functional groups, producing synthetically valuable intermediates.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Applied
Bo Zhang, Fritz E. Kuehn
JOURNAL OF ENERGY CHEMISTRY
(2023)
Article
Chemistry, Organic
Sebastian Fischer, Terrence-Thang H. Nguyen, Andreas Ratzenboeck, Huw M. L. Davies, Oliver Reiser
Summary: A stereoselective, solvent- and metal-free method for endocyclic C-C bond cleavage of monocyclopropanated cyclopentadienes mediated by strong acids has been developed. It leads to the formation of highly functionalized six-membered carbocycles with high stereocontrol. The critical step involves the formation of a cyclopropyl carbocation that undergoes endocyclic ring opening through an SN2'-type attack of various nucleophiles. Subsequent synthetic transformations demonstrate the versatility of the resulting cyclohexenes for the synthesis of compounds with nonconventional substitution patterns.
Article
Chemistry, Organic
Daniel Dobler, Michael Leitner, Peter Kreitmeier, Oliver Reiser
Summary: An atom-efficient method for synthesizing 2-pyrone on a multigram scale was developed using a large-scale thermal rearrangement of cyclopentadienone epoxide as the key step. This approach also provides easy access to 6-substituted 2-pyrone natural product derivatives.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Sujittra Paenkaew, Usana Mahanitipong, Metha Rutnakornpituk, Oliver Reiser
Summary: A thermoresponsive and recyclable nanomaterial was synthesized by modifying magnetite nanoparticles (MNPs) with poly(N-isopropylacrylamide-co-diethylaminoethyl methacrylate) (P(NIPAAm-co-DEAEMA)), which contained thermoresponsive PNIPAAm and catalyst binding PDEAEMA. Pd nanoparticles were incorporated into this material, creating a nanocatalyst that exhibited high catalytic activity for the hydrogenation of olefins and nitro compounds with turnover frequencies (TOFs) up to 750 h-1. The catalyst maintained consistent catalytic activity over 10 consecutive runs by performing the hydrogenation above the lower critical solution temperature (LCST) of the copolymer (37 degrees C) and then cooling below the LCST (15 degrees C).
Article
Chemistry, Multidisciplinary
Tirtha Mandal, Narenderreddy Katta, Hendrik Paps, Oliver Reiser
Summary: This paper presents a sequential photocatalytic strategy that combines Cu(II)/Cu(I)-catalytic cycles for the oxoallylation of vinyl arenes using a-haloketones. Initially, Cu(II)-photocatalyzed oxohalogenation generates halide radicals from acyl halides, utilizing air as an oxidant, and can be used for late-stage modification of pharmaceuticals and agrochemicals. The subsequent one-pot Cu(I)-photocatalyzed allylation of a-bromoketones proceeds with high regio- and chemoselectivity, unaffected by the electronic nature of the styrenes.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Physical
Tim P. Schlachta, Greta G. Zambo, Michael J. Sauer, Isabelle Rueter, Carla A. Hoefer, Serhiy Demeshko, Franc Meyer, Fritz E. Kuehn
Summary: A comparative study was conducted to investigate the influence of electronic variations on the catalytic performance of three iron(II) NHC epoxidation catalysts. Different ligands were used to prepare the complexes, which were characterized using various methods. The results showed that a lower electron density at the iron atom led to a decline in epoxidation activity, while a more electron rich iron center did not necessarily result in higher activity due to reduced catalyst stability. Addition of Lewis acids significantly improved both activity and stability of the catalysts.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Oliver Reiser
Summary: Photocatalysis has become a powerful strategy for selective functionalization of molecules through radical intermediates. While iridium or ruthenium-based photocatalysts have been well-studied, the use of earth-abundant metal-based photocatalysts is less explored. Recently, the concept of light-induced homolysis using earth-abundant 3d-metal complexes has gained significant interest despite their short excited-state lifetimes. Cu(ii)-complexes play a prominent role in this concept and recent developments in organic synthesis showcase the future prospects of this growing field.
Review
Chemistry, Multidisciplinary
Tim P. P. Schlachta, Fritz E. E. Kuehn
Summary: Cyclic iron tetracarbenes are a class of macrocyclic iron N-heterocyclic carbene (NHC) complexes, inspired by heme analogs but with different electronic properties. The modification of their ligand framework allows control over the structural and electronic properties of the complexes. These iron tetracarbene complexes exhibit unique reactivity, involving the isolation of uncommon iron(iii) and iron(iv) species. They have been successfully applied in various catalytic reactions, such as C-H activation, CO2 reduction, aziridination, and epoxidation. This review provides insights for researchers to evaluate the properties of their complexes and optimize catalyst properties through ligand design.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Greta G. Zambo, Johannes Mayr, Michael J. Sauer, Tim P. Schlachta, Robert M. Reich, Fritz E. Kuehn
Summary: The synthesis and characterization of a novel macrocyclic and abnormally coordinating, mesoionic N-heterocyclic carbene iron complex are reported. The complex exhibits strong sigma-donor ability of the carbene moieties, indicating efficient catalytic activity in oxidation reactions. Initial tests on the epoxidation of cis-cyclooctene validate the assumption.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Alexander D. Boeth, Michael J. Sauer, Walter Baratta, Fritz E. Kuehn
Summary: The bis-abnormal N-heterocyclic carbene (aNHC) ruthenium complexes showed high catalytic activity in transfer hydrogenation and Oppenauer-type oxidation reactions. The order of reactivity was found to be influenced by steric effects.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
