Article
Chemistry, Multidisciplinary
Hanling Bao, Yabei Wu, Yuhang Jiang, Hao Zhang, Zhiyong Wang
Summary: This study investigates the effects of reduction and oxidation on the reactivity and regioselectivity of metallofullerene La@C-82 in Diels-Alder reaction. It is found that oxidation enhances the reactivity and changes the regioselectivity of the reaction. Energy decomposition analysis reveals that kinetic reactivity of the metallofullerene is determined by exchange-repulsion interaction energy.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Organic
Ruyu Xie, Zhiqiang Zhao, Yongxing Zhao, Rui Li, Jinzhong Yao, Maozhong Miao
Summary: Via Cu(I)-catalyzed cycloisomerization, readily available allenyl ketones bearing a cyclopropyl moiety can form in situ furan-fused cyclobutenes, which are highly reactive and powerful species that can undergo annulative fragmentation with terminal ynones to produce a wide variety of functional furans in moderate to high yields. This ring-distortion protocol features an unprecedented strain-controlled cycloisomerization/Diels-Alder/retro-Diels-Alder (CDRD) sequence under mild conditions.
Article
Biochemistry & Molecular Biology
Petar Strbac, Anamarija Bris, Davor Margetic
Summary: In this study, the first representative of isoindoles containing guanidine functionality, N,N'-Di-Boc-2H-isoindole-2-carboxamidine, was synthesized and its cycloaddition reactivity was investigated. The results showed that the title compound exhibited higher reactivity and the substitution with fluorine or guanidine functionality did not alter the reactivity of isoindoles, which was in accordance with computational results.
Article
Chemistry, Organic
Jian-Xiang Zhu, Fu Pi, Teng Sun, Wen-Yu Huang, Lu Gao, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: This article introduces a palladium-catalyzed tandem reaction that proceeds through sequential 2,4-dienylation/Michael addition/pi-sigma-pi isomerization/allylic alkylation. Using ortho-functionalized aryl enones and 2,4-dienyl carbonates as substrates, enantioenriched architectures with fused and spirocyclic frameworks are constructed in moderate to excellent yields and stereoselectivity. Importantly, the intrinsic intramolecular Diels-Alder reaction pattern of the dienylated intermediates is effectively reversed via Pd(0)-pi-Lewis base catalysis.
Review
Chemistry, Multidisciplinary
Razvan C. Cioc, Marc Crockatt, Jan C. Waal, Pieter C. A. Bruijnincx
Summary: This article introduces biomass-derived furanic platform molecules as promising building blocks for renewable chemicals and functional materials, and explores the application of Diels-Alder cycloaddition in converting these renewable resources in an efficient way. The importance of understanding the interplay between kinetics and thermodynamics in the cycloaddition reactions is emphasized, and relevant examples and research findings are provided.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhimei Mao, Aimin Huang, Lin Ma, Min Zhang
Summary: A facile visible light-promoted approach has been developed for the synthesis of anthracenone-furans from readily available 2,3-dibromonaphthoquinones and phenylbenzofurans via a formal Diels Alder reaction. This reaction involves wavelength-selective agitation of 4CzIPN, energy transfer to quinones, recombination of 1,6-biradicals, and elimination to give anthracenone-furans in good to excellent yields in one pot.
Article
Chemistry, Organic
David M. Malouf, Abigail D. Richardson, Scott J. L'Heureux, Elizabeth A. McDonough, Ava M. Henry, Jerry Y. Sheng, Erica A. Medhurst, Angel E. Canales, Cameron J. Fleischer, Ty B. Cecil, Spencer E. Thurman, Cameron C. McMullen, Philip J. Costanzo, Daniel A. Bercovici
Summary: In this study, Ylidenenorbornadienes (YNDs) were prepared by [4 + 2] cyclo-additions and were found to react with beta-mercaptoethanol to yield a mixture of four diastereomers. These diastereomers exhibited retro-[4 + 2] cycloaddition at different rates. The rate constants of the diastereomers were extrapolated using a simulated kinetics approach. The fragmentation of YNDs showed a wide variability in rate, depending on the stereoelectronics of the ylidene substituents. Notably, a substrate containing one carboxylic ester exhibited exceptional stability to fragmentation.
Article
Chemistry, Multidisciplinary
I van Scodeller, Karine De Oliveira Vigier, Eric Muller, Changru Ma, Frederic Guegan, Raphael Wischert, Francois Jerome
Summary: In this study, a Diels-Alder/aromatization sequence is used to synthesize renewable aromatics from bio-based furfural derivatives and inexpensive alkenes. The control of ortho/meta selectivity in the Diels-Alder step is crucial for developing a wide range of renewable aromatics. Experimental and theoretical approaches show that ortho and meta cycloadducts are kinetic and thermodynamic products, respectively, and the feasibility of the reaction is significantly impacted by substituents on the reactants.
Article
Biochemistry & Molecular Biology
Gangming Xu, Suiqun Yang
Summary: Natural [4 + 2]-cyclases play a crucial role in the biosynthesis of natural products, with microbial [4 + 2]-cyclases exhibiting structural diversity and a broad substrate range. The evolutionary history and catalytic mechanisms of these cyclases, with 52 characterized so far, remain unclear.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2021)
Article
Chemistry, Multidisciplinary
Masao Ohashi, Dan Tan, Jiayan Lu, Cooper S. Jamieson, Daiki Kanayama, Jiahai Zhou, K. N. Houk, Yi Tang
Summary: The synthesis of cis-decalin structures using [4 + 2] cycloaddition with high stereoselectivity is challenging. In this study, we investigated the biosynthetic pathway of the fungal natural product fischerin (1) and identified a novel pericyclase, FinI, which catalyzes this reaction. The cocrystal structure of FinI, a predicted O-methyltransferase, with the product and SAM provides valuable insights into the natural formation of cis-decalin.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Albert Artigas, Cristina Castanyer, Nil Roig, Agusti Lledo, Miquel Sola, Anna Pla-Quintana, Anna Roglans
Summary: A synthetic methodology for functionalizing C-60 and C-70 fullerenes by cascading reactions has been reported. The resulting polyheterocyclic fullerene adducts can be potentially used in organic and perovskite photovoltaic devices.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Guang-Chao Feng, Jun-Chi Li, Xiang Huang, Ji-Kai Liu, Bin Wu, Jin-Ming Yang
Summary: A novel cascade gold(I)-catalyzed hydroarylation of alkynylindoles and subsequent Diels-Alder cycloaddition with electron-deficient alkynes and alkenes is reported herein. The method features low catalyst loadings, high regioselectivity, broad functional group tolerances, access to important heterocycles, and 100% atom economy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
John B. Bauer, Fatima Diab, Cacilia Maichle-Mossmer, Hartmut Schubert, Holger F. Bettinger
Summary: The study investigates the Diels-Alder reaction between different bisdiene building blocks and a synthetic compound, revealing variations in diastereoselectivity and the formation of different orientations of diastereomers. The all-syn diastereomer can be transformed into a molecular belt through inter- and intramolecular reactions, serving as a synthetic intermediate for the synthesis of a [11]cyclacene photoprecursor.
Article
Chemistry, Organic
Julia O. Strelnikova, Alexander N. Koronatov, Nikolai Rostovskii, Alexander F. Khlebnikov, Olesya Khoroshilova, Mariya A. Kryukova, Mikhail S. Novikov
Summary: The domino reaction catalyzed by Rh-2(Piv)(4) leads to the formation of N-sulfonylated (Z)-2-(2-aminovinyl)imidazoles, providing a direct and flexible access to the desired compounds.
Article
Chemistry, Multidisciplinary
Enric Sabater, Miquel Sola, Pedro Salvador, Diego M. Andrada
Summary: The classic dichotomy between nitrogen and its heavier congeners is discussed in the context of encapsulation of phosphorus compounds in fullerene cages. Computational studies show that fullerene structures C-70 to C-100 can encapsulate P-2 molecules with intact triple bonds, excluding P-4. Thermodynamic analysis confirms the favorable nature of the encapsulation process.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Silvia Escayola, Nathalie Proos Vedin, Albert Poater, Henrik Ottosson, Miquel Sola
Summary: In addition to the common π-ring aromaticity, certain compounds also display σ-aromaticity formed by substituents. This study explores the double aromaticity in substituted tropylium cations and finds that only a specific functional-dependent system satisfies the conditions for double aromaticity.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mayukh Bhadra, Therese Albert, Alicja Franke, Verena Josef, Ivana Ivanovic-Burmazovic, Marcel Swart, Pierre Moenne-Loccoz, Kenneth D. Karlin
Summary: Transition-metal-mediated reductive coupling of nitric oxide (NO(g)) to nitrous oxide (N2O(g)) is significant in various fields. In this study, a detailed mechanism of NO(g) reductive coupling at a copper-ion center was elucidated using density functional theory (DFT). The reaction pathway and intermediates were studied in different solvents, and metastable species were characterized using spectroscopic techniques. The findings provide a comprehensive understanding of NO(g) activation at a reduced Cu site and its implications in different environments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
G. George, O. A. Stasyuk, A. A. Voityuk, A. J. Stasyuk, M. Sola
Summary: Pi-conjugated organic molecules have a wide range of exciting applications in batteries, solar cells, and light-emitting diodes. Among these, antiaromatic compounds are of particular interest due to their smaller energy gap, which facilitates charge transfer. This study explores the ground and excited-state properties of two nitrogen-doped nanohoops and their complexes with C-60 fullerene, showing different behavior depending on aromaticity. The results suggest that antiaromatic compounds have a longer charge transfer state lifetime compared to aromatic compounds.
Review
Chemistry, Physical
Sergio Posada-Perez, Miquel Sola, Albert Poater
Summary: The increasing concentration of anthropogenic CO2 in the air is leading to global warming. The Paris Agreement aims to reduce greenhouse gas emissions, with CO2 conversion being a key strategy. The use of metal-supported nanoparticles as catalysts for CO2 conversion is discussed, with a focus on the potential of single-metal-atom deposition and the importance of NP size, metal-support interactions, and vacancy formation.
Article
Chemistry, Physical
Jordi Vila, Miquel Sola, Thierry Achard, Stephane Bellemin-Laponnaz, Anna Pla-Quintana, Anna Roglans
Summary: This article describes the [2 + 2 + 2] cycloaddition of 1,5-bisallenes and alkynes under the catalysis of Rh(I) with hemilabile thioether-functionalized N-heterocyclic carbene ligands. This method effectively provides access to different trans-5,6-fused bicyclic systems with two exocyclic double bonds in the cyclohexene ring. The complete mechanism of this transformation as well as the preference for the trans-fusion over the cis-fusion has been rationalized by density functional theory calculations.
Review
Chemistry, Inorganic & Nuclear
Jesus Antonio Luque-Urrutia, Thalia Ortiz-Garcia, Miquel Sola, Albert Poater
Summary: In this review, the author discusses how the burning of fossil fuels is driving the need for green energy. The overuse of non-renewable resources and the lack of recycling efforts have created an unsustainable situation that is leading to climate change. The article explores various methods, such as catalysts for using water or alcohols as energy sources, the recycling of gases like CO2 and N2O, and non-catalytic means of generating energy through solar cell production.
Review
Multidisciplinary Sciences
Qin Zhu, Shuwen Chen, Dandan Chen, Lu Lin, Kui Xiao, Liang Zhao, Miquel Sola, Jun Zhu
Summary: This review highlights the relationship between aromaticity and reaction mechanism, emphasizing the importance of computational chemistry in understanding aromaticity-driven reactions. Aromatizing a transition state/product or destabilizing a reactant by antiaromaticity can promote specific reactions. The article also discusses various specific reaction examples, including small-molecule activation, bond activation, rearrangement, and metathesis reactions.
FUNDAMENTAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Anna Vidal-Lopez, Sergio Posada-Perez, Miquel Sola, Albert Poater
Summary: CO2 is the main contributor to the greenhouse effect and global warming, and reducing its concentration in the atmosphere is a major challenge. This study uses density functional theory to investigate the potential use of Au-1@g-C3N4 electrocatalyst for transforming CO2 into valuable products. The simulations reveal that methane is the main product after eight proton-electron transfers. This computational study provides insights into finding suitable electrocatalysts for CO2 reduction that are cost-effective and stable.
CHEMISTRY-SWITZERLAND
(2023)
Article
Chemistry, Multidisciplinary
Kazuki Nakanishi, Leonardo I. Lugo-Fuentes, Jun Manabe, Ronghao Guo, Soichi Kikkawa, Seiji Yamazoe, Kenji Komaguchi, Shoko Kume, Dariusz W. Szczepanik, Miquel Sola, J. Oscar C. Jimenez-Halla, Sadafumi Nishihara, Kazuyuki Kubo, Masaaki Nakamoto, Yohsuke Yamamoto, Tsutomu Mizuta, Rong Shang
Summary: This work reports the oxidation behavior of an all-carbon-ligated iridium complex and successfully synthesizes a high-valent iridium complex bearing a CCCC-tetradentate ligand. These results close a synthetic gap for carbon-ligated iridium complexes and demonstrate the electronic tuning potential of organic pi ligands for unusual electronic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jordi Poater, Clara Vinas, Silvia Escayola, Miquel Sola, Francesc Teixidor
Summary: This study provides experimental and computational evidence that the C-C bond formed between two adjacent carbons that lose H atoms in o-carboryne is different from that in o-benzyne. While the C-C bond in o-benzyne behaves as a triple bond, the C-C bond in o-carboryne is a double bond. Therefore, 1,2-dehydro-o-carboryne should be called o-carborene instead of o-carboryne.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Multidisciplinary Sciences
Jordi Poater, Pascal Vermeeren, Trevor A. A. Hamlin, F. Matthias Bickelhaupt, Miquel Sola
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Dominic Shiels, Magda Pascual-Borras, Paul G. Waddell, Corinne Wills, Josep-Maria Poblet, R. John Errington
Summary: A novel isopolyoxotungstate has been identified after 30 years since its initial spectroscopic evidence. The heptatungstate [W7O24H](5-) features a stable structure with a fused {W-5} lacunary Lindqvist unit and a ditungstate fragment, being the third isopolytungstate obtained from non-aqueous systems.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
G. George, O. A. Stasyuk, M. Sola, A. J. Stasyuk
Summary: Belt-shaped aromatic compounds are among the most attractive classes of radial pi-conjugated nanocarbon molecules. We propose rules for their design with improved electron-donating properties.
Article
Chemistry, Inorganic & Nuclear
Daniel E. Trujillo-Gonzalez, Gerardo Gonzalez-Garcia, J. Oscar C. Jimenez-Halla, Miquel Sola
Summary: This study investigates the ability of beryllium compounds to activate C-X bonds and finds that bidentate ligands play a key role in providing the necessary electrons.
DALTON TRANSACTIONS
(2023)
