Article
Chemistry, Applied
Tao Wang, Bo Huang, You-Qing Wang
Summary: Using chiral phosphoric acids as organocatalysts, a formal asymmetric (4+2) cycloaddition of 3-methylene isoindolinone and in situ-generated ortho-quinone methide substrates is achieved. This reaction allows the construction of spiro chroman-isoindolinones containing spiro-N,O-heterocycles with high enantioselectivity, with a broad substrate scope.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yuan-Yuan Xu, Zhong-Hua Gao, Cao-Bo Li, Song Ye
Summary: The enantioselective alpha-oxidative coupling of enals with carboxylic acids was achieved by umpolung of an NHC-bound enolate with an iodine(III) reagent. The reaction produced alpha-acyloxyl-beta,gamma-unsaturated esters in good yields, with high regio- and enantioselectivities. The reaction involved the formation of an enol iodine(III) intermediate from the enolate with iodosobenzene, which changed the polarity of the enal's alpha-carbon from nucleophilic to electrophilic and facilitated the subsequent carboxylate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nagarajan Ramkumar, Larisa Baumane, Dzintars Zacs, Janis Veliks
Summary: A simple process for the oxy-monofluoromethylation of alkenes is presented. The use of visible-light copper(I) photoredox catalysis, in combination with an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands, enables the synthesis of gamma-fluoro-acetates from various olefinic substrates under mild conditions. The study also demonstrates its applications in late-stage diversification of complex molecules, amino acids, and the synthesis of fluoromethylated heterocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Vibha V. Kanale, Christopher Uyeda
Summary: Cobalt catalysts facilitate highly enantioselective ring-opening reactions of 2,5-dihydrofurans using vinylidenes. The resulting products are acyclic organozinc compounds, capable of further functionalization with an electrophile. The proposed mechanism involves the formation of a cobalt vinylidene species that adds to the alkene via a [2+2]-cycloaddition pathway, followed by ring-opening through outer-sphere & beta;-O elimination assisted by a ZnX2 Lewis acid. DFT models explain the observed stereochemical outcome by suppressing competing inner-sphere syn & beta;-H and & beta;-O elimination pathways due to the geometric constraints of the metallacycle intermediate. Cobalt catalysts also promote enantioselective ring-opening reactions of unstrained heterocycles via reductive addition of 1,1-dichloroalkenes. The resulting products are acyclic homoallylic alcohols with a vinylzinc motif, which can be further modified with an electrophile. Mechanistic studies suggest that the ring-opening occurs through outer-sphere & beta;-O elimination facilitated by a Zn(II) Lewis acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Arghya Banerjee, Satavisha Sarkar, Jagrut A. Shah, Nicoline C. Frederiks, Emmanuel A. Bazan-Bergamino, Christopher J. Johnson, Ming-Yu Ngai
Summary: The study presents a visible-light-induced copper catalysis for the production of diverse heterocycles, with high tolerance to various functional groups. Preliminary mechanistic investigation suggests a cooperative action of two catalysts under visible-light irradiation to facilitate the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Min Zheng, Ke Gao, Haitao Qin, Guigen Li, Hongjian Lu
Summary: Chemodivergent asymmetric synthesis was achieved by tuning the metal-to-ligand ratio in an organometallic catalytic system. The study demonstrated high efficiency and enantioselectivity in the asymmetric transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yuchen Wu, Takuma Sasayama, Takahiro Gotoh, Mamoru Ito, Takanori Shibata
Summary: In this study, hexaazatruxenes were successfully synthesized and their potential as light-emitting materials and building blocks was demonstrated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jessica C. Bieniek, Boris Mashtakov, Dieter Schollmeyer, Siegfried R. Waldvogel
Summary: This study presents an electrocatalytic method using hypervalent iodine(III) as a mediator to synthesize 1H-N-aryl-3,4-dihydroquinolin-2-ones by C-N bond formation. The method features a low catalyst loading, recycling of the solvent, and is a sustainable alternative to conventional approaches.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tobias Wagener, Lukas Lueckemeier, Constantin G. Daniliuc, Frank Glorius
Summary: This study successfully demonstrates the synthesis of sought-after, enantioenriched delta-lactams through an interrupted hydrogenation mechanism using oxazolidinone-substituted pyridines and water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Melania Gomez-Martinez, Maria del Carmen Perez-Aguilar, Dariusz G. Piekarski, Constantin G. Daniliuc, Olga Garcia Mancheno
Summary: An enantioselective anion-binding organocatalytic approach using versatile N,N-dialkylhydrazones as polarity-reversed nucleophiles is presented. A highly ordered hydrogen-bond network was envisioned between a CF3-substituted triazole-based multidentate HB-donor catalyst, the ionic substrate, and the hydrazone in a supramolecular chiral ion-pair complex. Experimental and computational studies supported the formation of this network, showing the crucial role of the anion as a template unit. The asymmetric reaction provided highly enantiomerically enriched hydrazones that could be further derivatized to value-added compounds with up to three stereocenters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Balazs L. Toth, Gergo Salyi, Attila Domjan, Orsolya Egyed, Attila Benyei, Zsombor Gonda, Zoltan Novak
Summary: The study reports a stereoselective procedure for direct fluorovinylation of aromatic and heteroaromatic scaffolds utilizing palladium-catalyzed ortho C-H activation reaction of aniline derivatives. The use of non-symmetrical aryl(fluoroalkenyl)-iodonium salts as fluoroalkenylating agents allows mild reaction conditions, and feasibility has been demonstrated through over 50 examples.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Yasuaki Fukazawa, Vladimir Yu. Vaganov, Julia V. Burykina, Artem N. Fakhrutdinov, Ruslan I. Safiullin, Felix Plasser, Aleksandr E. Rubtsov, Valentine P. Ananikov, Andrei V. Malkov
Summary: The mechanism of metal-catalyzed asymmetric alkylation of indoles remains uncertain. In this study, the authors investigate the mechanism from both molecular and nano-level perspectives, revealing the role of water and catalyst precursor on reaction selectivity and performance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Qinglin Zhang, Kang Liang, Chang Guo
Summary: A novel electrolytic system has been introduced to divert standard ionic reactivity, providing a brand-new pattern of reactivity-electricity-driven asymmetric catalysis, which serves as a privileged chiral platform for enantioselective radical allylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kumar Bhaskar Pal, Ester Maria Di Tommaso, A. Ken Inge, Berit Olofsson
Summary: We report an efficient radical-mediated C-C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C-C bond formation is stereospecific and proceeds through a concerted radical coupling transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Maxime Denis, Samuel Blais, Sylvain Canesi
Summary: A stereoselective synthesis of isolycoricidine, a natural product belonging to the Amaryllidaceae alkaloids family, was achieved. The study also conducted a synthetic investigation on the main core of lycoricidine, resulting in the formation of analogues and a diastereomer of dihydrolycoricidine. The research utilized various strategies including oxidative phenol dearomatization, stereoselective Heck process, selective dihydroxylation, stereoselective reductions, and oxidative retro-Michael procedure as an amine-deprotecting group strategy. In addition, the study highlighted the usefulness of hypervalent iodines in total synthesis of natural products.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Francisco Nunez-Zarur, Aleix Comas-Vives
Summary: The study found that Cr(III) sites with higher strain are less active, and ethylene insertion into the Cr-O bond is more favorable than C-H bond activation for ethylene polymerization initiation. Activation energies for both initiation mechanisms are controlled by both interaction and strain energies.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Applied
C. S. Praveen, A. Comas-Vives
Summary: The study focuses on evaluating the catalytic trends of PDH for four M(III) single-sites on amorphous SiO2, finding that Ga and Cr show comparable catalytic activity to experimental levels, serving as benchmarks for the model and methodology used. Additionally, In(III) and Mo(III) on SiO2 are identified as potential active catalysts for PDH, provided they can be synthesized and stable under reaction conditions.
TOPICS IN CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Yannick Kraemer, Emily Nicole Bergman, Antonio Togni, Cody Ross Pitts
Summary: In the development of synthetic methods, researchers discovered a mild and inexpensive oxidative fluorination method based on potassium fluoride and trichloroisocyanuric acid (TCICA), which enabled the synthesis of pentafluorosulfanyl (SF5) compounds. Further exploration led to the discovery of its application in the synthesis of other fluorinated heteroatoms. Ultimately, it was found that this method can be used to synthesize SF5Cl.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Subrata Patra, Ivan Mosiagin, Rahul Giri, Dmitry Katayev
Summary: The development and application of organic nitrating reagents are of great importance for the preparation of various drugs, agrochemicals, and materials. These reagents provide chemists with a practical and direct way to access nitro compounds. They enhance reactivity and allow nitration to be carried out in an ecofriendly and sustainable manner.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Rahul Giri, Ivan Mosiagin, Ivan Franzoni, Nicolas Yannick Noetel, Subrata Patra, Dmitry Katayev
Summary: In this study, a simple, mild, and switchable protocol was developed to access various gem-difluoro compounds using chlorodifluoroacetic anhydride as a versatile and cost-effective reagent. The mechanism of the reaction was also investigated, demonstrating the advantages of this method in terms of product selectivity and reaction applicability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Rahul Giri, Subrata Patra, Dmitry Katayev
Summary: We developed a practical photocatalytic strategy for the synthesis of various nitro-containing cyclic compounds from olefins. This process involves semipinacol-type rearrangement, cycloetherification, and lactonization reactions, using N-nitrosuccinimide as a stable non-metallic nitrating reagent. The reaction proceeds through a light-driven mechanism mediated by a photoredox catalyst, involving NO2 radical pathway and N-N bond fragmentation. This reaction shows excellent compatibility with different functional groups and structural variations under mild reaction conditions.
Article
Chemistry, Physical
Lole Jurado, Jerome Esvan, Ligia A. A. Luque-Alvarez, Luis F. F. Bobadilla, Jose A. Odriozola, Sergio Posada-Perez, Albert Poater, Aleix Comas-Vives, M. Rosa Axet
Summary: Rhodium-catalysed hydroformylation is an effective tool for both bulk and fine-chemical synthesis, but its major drawbacks are metal leaching and catalyst recycling. Single-atom catalysts have emerged as a powerful solution to combine the advantages of homogeneous and heterogeneous catalysts. In this study, we demonstrate that Rh atoms anchored on graphitic carbon nitride are robust catalysts for the hydroformylation reaction of styrene.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Subrata Patra, Ivan Mosiagin, Rahul Giri, Thomas Nauser, Dmitry Katayev
Summary: This paper introduces an electrochemically assisted method for generating nitryl radicals from ferric nitrate using inexpensive graphite and stainless-steel electrodes under mild reaction conditions. The reaction mechanism is supported by spectroscopic and experimental studies. The synthesis of diverse products is demonstrated through the development of highly efficient nitration protocols for various unsaturated hydrocarbons. These protocols have broad applications, are easily scalable for large quantities, and exhibit exceptional substrate generality and functional-group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wenjuan Zhang, Anna Vidal-Lopez, Aleix Comas-Vives
Summary: This study evaluates the catalytic activity of single-atom catalysts (SACs) based on Cu and Fe supported on Mo2C in the reverse water-gas shift (RWGS) mechanism using DFT calculations. The study finds differences in reactivity between Cu and Fe, with Cu/Mo2C showing lower energy barriers for CO formation and Fe/Mo2C showing lower energy barriers for H2O formation. Oxygen coverage is found to impact the reactivity, and Fe/Mo2C is suggested as a potentially active RWGS catalyst based on theoretical calculations.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ivan Mosiagin, Anthony J. Fernandes, Alena Budinska, Liana Hayriyan, Kai E. O. Ylijoki, Dmitry Katayev
Summary: This study reports an efficient, mild, and catalytic ipso-nitration method of organotrimethylsilanes using an electrophilic N-nitrosaccharin reagent. The method allows chemo-selective nitration under mild reaction conditions and exhibits remarkable substrate generality and functional group compatibility. The reaction conditions are orthogonal to other common functionalities, allowing programming of molecular complexity via successive transformations or late-stage nitration. Detailed mechanistic investigation supports a classical electrophilic aromatic substitution mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tharinee Theerathanagorn, Anna Vidal-Lopez, Aleix Comas-Vives, Albert Poater, Valerio D'Elia
Summary: The study demonstrates that water-soluble organocatalysts can efficiently synthesize cyclic carbonates from CO2 and various epoxides in water-organic biphasic systems. The addition of simple inorganic salts accelerates the reaction rates and seawater is particularly effective as the aqueous layer. Control experiments and DFT calculations provide insights into the heterogeneous catalytic process at the interface between water droplets and the epoxide phase.
Article
Chemistry, Physical
Estefania Diaz Lopez, Aleix Comas-Vives
Summary: This study evaluated Rh(111)-catalyzed dry reforming of methane (DRM) using density functional theory and kinetic Monte Carlo simulations. The results showed that the catalytic system displayed Arrhenius behavior with CO2 activation identified as the dominant step.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Andreas Mueller, Aleix Comas-Vives, Christophe Coperet
Summary: The direct hydrogenation of CO or CO2 to methanol is an important research area in sustainable development. This study investigates the alloying and surface formation of Cu-based catalysts with Ga and Zn promoters using periodic DFT calculations and ab initio thermodynamics. The results show that under CO2 hydrogenation conditions, the promoters undergo partial dealloying and oxidation, while under CO hydrogenation conditions, the surface is fully reduced and alloyed. The preferred state of the catalyst is influenced by the gas phase composition, leading to different catalytic activity and stability.
Article
Chemistry, Physical
Jan L. Alfke, Andreas Mueller, Adam H. Clark, Antonio Cervellino, Milivoj Plodinec, Aleix Comas-Vives, Christophe Coperet, Olga Safonova
Summary: Highly unusual BCC-structured Cu nanoparticles were detected as a transient intermediate during the H-2 reduction process. DFT calculations show that the BCC-Cu phase is more stable for small particles and increases stability at lower H-2 concentrations. The synthesis of stable BCC-structured Cu nanoparticles was achieved through reduction of the same grafted precursor either in 10% H-2 diluted in Ar or 100% H-2 at low temperature.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Estefania Diaz Lopez, Aleix Comas-Vives
Summary: In this study, we investigated the dry reforming of methane catalyzed by the Ru (0001) surface using first-principles calculations and kinetic Monte Carlo simulations. Our results from periodic density functional theory (DFT)-based calculations revealed the energy barriers for CO2 dissociation, CO2 cleavage, and CH4 activation. The kinetic Monte Carlo simulations considered different adsorption sites and showed that the DRM reaction predominantly proceeds through the C* + O* route. Moreover, increasing the temperature resulted in higher turnover frequency and changed the coverage of species on the catalytic surface.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
