Review
Chemistry, Physical
Ummareddy Venkata Subba Reddy, Bheemreddy Anusha, Zubeda Begum, Chigusa Seki, Yuko Okuyama, Michio Tokiwa, Suguru Tokiwa, Mitsuhiro Takeshita, Hiroto Nakano
Summary: Chiral primary alpha-amino amides, as bifunctional organocatalysts, have been widely used in various asymmetric organic transformations due to their advantageous characteristics, such as low cost, easy synthesis, and the ability to incorporate diverse functional groups.
Article
Chemistry, Applied
Jasper S. Moehler, Lena K. Beiersdoerfer, Brenno Masina, Philipp Wechsler, Helma Wennemers
Summary: N-heterocyclic moieties are commonly found in pharmaceuticals and agrochemicals, but pose a challenge for metalorganic and organocatalytic transformations. This study presents tripeptide catalysts for stereoselective conjugate addition reactions between N-heterocyclic substituted aldehydes and electrophiles, achieving high yields and selectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Celine Nieuwland, Celia Fonseca Guerra
Summary: The amino groups of thio- and selenoamides can act as stronger hydrogen-bond donors than of carboxamides, and this is determined by the steric size of the chalcogen atom rather than the electronegativity or polarizability.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Amila M. Abeysekera, Boris B. Averkiev, Abhijeet S. Sinha, Pierre Le Magueres, Christer B. Aakeroy
Summary: The study found that intramolecular hydrogen bonds in some co-crystals remained intact, while most intermolecular hydrogen bonds in the targets were disrupted. The acceptor sites selected by the halogen bond donors were mainly distributed in N(pyr), O=C, or pi sites.
Article
Chemistry, Multidisciplinary
Hyo-Jun Lee, Keiji Maruoka
Summary: This article provides detailed insights into the applications of four types of amino Tf-amide catalysts in asymmetric transformations, including stereoselective reactions catalyzed by enamine intermediates, asymmetric direct Mannich reactions catalyzed by aliphatic Tf-amides, asymmetric direct aldol reactions and conjugate additions catalyzed by primary-amino aliphatic Tf-amides, and asymmetric transformations catalyzed by modified amino aromatic Tf-amides.
Article
Chemistry, Physical
Yuanyuan Sun, Ying Li, Xiaoyan Li, Yanli Zeng
Summary: In this study, the catalytic mechanism of mono/bis(iodoimidazolium) halogen bond donor catalysts in the Michael addition reaction was investigated. It was found that bis(iodoimidazolium) halogen bond donor catalysts showed good catalytic performance and could accelerate the reaction. The catalyzed reaction involves two steps, with two possible pathways for proton transfer, where the indirect pathway is more likely to occur.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Diksha Gambhir, Sanjay Singh, Ravi P. Singh
Summary: The rational combination of two catalysts has been widely used in the synthesis of biologically and pharmacologically relevant chiral compounds. This review article focuses on the achievements in asymmetric catalysis and synthesis using enamine and iminium-based dual organocatalytic systems. The combination of enamine/iminium catalysis with other organocatalytic systems has paved the way for the construction of complex chiral compounds.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Victor Laina-Martin, Jorge Humbrias-Martin, Ruben Mas-Balleste, Jose A. Fernandez-Salas, Jose Aleman
Summary: A highly efficient enantioselective inverse-electron-demand aza-Diels-Alder reaction has been developed, allowing the synthesis of benzofuran-fused 2-piperidinol derivatives with three contiguous stereocenters in a highly selective manner. Density functional theory calculations support the reaction mechanism and reveal the mode of action of the hydrogen-bond donor.
Article
Multidisciplinary Sciences
Nagaraju Kerru, Naresh Kumar Katari, Sreekantha B. Jonnalagadda
Summary: The utilization of small organic compounds as catalysts, known as organocatalysis, has emerged as a dominant technique in organic conversions. Researchers have focused on designing simpler organocatalysts to synthesize chiral molecules with high yields. This article highlights the impact of different types of organocatalysts in organic synthesis and emphasizes the crucial methods to construct valuable molecules with high enantiomeric purity.
PHYSICAL SCIENCES REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
David A. McLeod, Mathias Kirk Thogersen, Casper Larsen Barlose, Mette Louise Skipper, Erlaitz Basabe Obregon, Karl Anker Jorgensen
Summary: This study presents a novel enantioselective (8+3) cycloaddition reaction using a chiral bifunctional Bronsted base catalyst. The reaction leverages an anionic activation strategy and differs from typical Lewis-acid activation protocols. Experimental and computational results support the relevance of this reaction and its potential application in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Dhananjoy Pal, Tim Steinke, Lukas Vogel, Elric Engelage, Sascha Heinrich, Dana Kutzinski, Stefan M. Huber
Summary: This article describes the synthesis of a mixed chalcogen- and halogen-bond donor and provides a first indication of its catalytic activity in a benchmark reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Le Li, Peter Mayer, David S. Stephenson, Armin R. Ofial, Robert J. Mayer, Herbert Mayr
Summary: The kinetics and mechanisms of the reaction between methyl diazoacetate and 1-(N-pyrrolidino)cycloalkenes were studied using NMR spectroscopy and DFT calculations. It was found that a previously unrecognized reaction pathway involving zwitterionic intermediates can be opened for stepwise cycloadditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Feng Zhu, Wenbin Zhang, Jiao Xun, Bi-Jun Geng, Qing-Man Liang, Yang Yang
Summary: This review focuses on the effects of proton donor/acceptor on several typical electrocatalytical reactions, including species, concentration, pKa, and steric hindrance. Specifically, the proton transfer pathway arising from ligand design strategy of molecular catalysts and modification of electrode-electrolyte interface is presented.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mariia Babkova, Rene Wilhelm
Summary: In this study, a series of new multifunctional organocatalysts were prepared and evaluated for the asymmetric aldol reaction of acetone and aromatic aldehydes. Several of the catalysts exhibited high catalytic activity and selectivity. The combination of camphor-based moiety and proline-based unit was found to be crucial for the performance of the catalysts.
Article
Chemistry, Multidisciplinary
Le Li, Robert J. Mayer, David S. Stephenson, Peter Mayer, Armin R. Ofial, Herbert Mayr
Summary: The kinetics and mechanism of reactions between methyl diazoacetate, dimethyl diazomalonate, 4-nitrophenyldiazomethane, and diphenyldiazomethane with sulfonium ylides and enamines were studied using UV-Vis and NMR spectroscopy. It was found that sulfonium ylides and enamines react with the terminal nitrogen of the diazo alkanes to form zwitterions, which undergo various subsequent reactions. The electrophilicity parameters of the diazo compounds were determined using the measured rate constants and known reactivity indices. This study provides important insights into this field of research.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Sagar R. Mudshinge, Yuhao Yang, Bo Xu, Gerald B. Hammond, Zhichao Lu
Summary: The first C-SCF3/SeCF3 cross-coupling reactions using gold redox catalysis are reported. The new method enables the one-stop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers, with a broad substrate scope. It is scalable and can be applied to late-stage functionalization of bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Atanu Modak, Juan Alegre-Requena, Louis de Lescure, Kathryn J. Rynders, Robert S. Paton, Nicholas J. Race
Summary: The ability to manipulate C-C bonds for selective chemical transformations is a challenging and growing area of research. The study reported a formal insertion of diazo compounds into unactivated C-C bonds of benzyl bromide derivatives catalyzed by a simple Lewis acid, resulting in products containing benzylic quaternary centers and alkyl bromides amenable to further derivatization. Computational analysis provided insight into the reaction mechanism, particularly the key selectivity-determining step.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Heidi Klem, Martin McCullagh, Robert S. Paton
Summary: Understanding enzymatic mechanisms is crucial for biologics development and enzyme design; Quantum mechanical potentials aid in studying complex enzymatic mechanisms; Dynamic interconversion of enzyme conformations poses challenges for computational models; Structural clustering bridges molecular dynamics and catalysis models effectively.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Juan V. Alegre-Requena, Stephen J. Sujansky, Spencer P. Pajk, Liliana C. Gallegos, Robert S. Paton, Jeffrey S. Bandar
Summary: This study investigates the mechanism of nucleophilic addition of alcohols to simple alkenes, revealing the influence of alcohol stoichiometry on reaction rate and proposing a new solution. The improved method does not require excess alcohol, expands the substrate scope, and utilizes more practical catalyst systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Pearse Solon, Mihai V. Popescu, Ji-Yuan Du, Robert Paton, Martin D. Smith
Summary: Controlling absolute stereochemistry in catalytic photochemical reactions is challenging. But recent studies have shown that selective excitation of the reaction substrate with a chiral catalyst can enable enantioselective triplet state reactions. In this study, researchers applied this approach to the enantioselective catalysis of a 6N photocyclization by designing an iridium photosensitizer that undergoes energy transfer to the reaction substrate only in the presence of a chiral Lewis acid complex. By tuning the photocatalyst, background reactivity can be suppressed and enantioselectivity improved.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Benjamin T. Boyle, Jeffrey N. Levy, Louis de Lescure, Robert S. Paton, Andrew McNally
Summary: This study reports a new method for pyridine halogenation reactions, which involves a reaction sequence of pyridyl ring opening, halogenation, and ring closing to achieve highly regioselective halogenation reactions on pyridine precursors. Experimental and computational mechanistic studies show that the nature of the halogen electrophile can modify the selectivity-determining step.
Article
Chemistry, Multidisciplinary
Ranjana Bisht, Mihai V. Popescu, Zhen He, Ameer M. Ibrahim, Giacomo E. M. Crisenza, Robert S. Paton, David J. Procter
Summary: Activated benzothiophenes undergo C-H/C-H-type coupling with phenols to give C4 arylation products without a directing group or a metal catalyst. Quantum chemical calculations propose a stepwise mechanism involving aryloxysulfur species cleavage and addition of phenoxonium cation to C4 position. The metal-free arylation process demonstrates varied selective manipulation of benzothiophene products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Matthew A. Horwitz, Alexander B. Durr, Konstantinos Afratis, Zijun Chen, Julia Soika, Kirsten E. Christensen, Makoto Fushimi, Robert S. Paton, Veronique Gouverneur
Summary: The controlled programming of regiochemical outcomes in nucleophilic fluorination reactions with alkali metal fluoride is achieved through two synergistic approaches exploiting hydrogen bonding catalysis. The charge density of fluoride is modulated with a hydrogen-bond donor urea catalyst to influence the kinetic regioselectivity in the fluorination of dissymmetric aziridinium salts. Additionally, a urea-catalyzed formal dyotropic rearrangement is reported, allowing access to enantioenriched fluoroamine regioisomers and providing new opportunities in regiodivergent asymmetric (bis)urea-based organocatalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Owen Smith, Mihai V. Popescu, Madeleine J. Hindson, Robert S. Paton, Jonathan W. Burton, Martin D. Smith
Summary: This paper reports the design, synthesis and characterization of a helically chiral triaryloxonium ion that functions as a determinant of configuration. It is the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre.
Article
Chemistry, Physical
Peng Zhang, Chang-Qiu Guo, Wang Yao, Chuan-Jun Lu, Yingzi Li, Robert S. S. Paton, Ren-Rong Liu
Summary: A palladium-catalyzed amination method was developed to construct structurally diverse N-C atropisomers, and the reaction mechanism was explained using density functional theory calculations. This method has a broad substrate scope, high stereoselectivity, a simple catalytic system, good functional group tolerance, and dynamic kinetic resolution.
Article
Chemistry, Multidisciplinary
Juan V. Alegre-Requena, Sowndarya S. Shree, Raul Perez-Soto, Turki M. Alturaifi, Robert S. Paton
Summary: AQME is a free and open-source Python package for automated workflows in cheminformatics and quantum chemistry. It integrates tasks across multiple computational chemistry packages and data formats, preserving computational protocols, data, and metadata for access and reuse. AQME has a modular structure and can be used by researchers familiar with Python.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jeong-Yu Son, Santeri Aikonen, Nathan Morgan, Alexander S. Harmata, Jesse J. Sabatini, Rosario C. Sausa, Edward F. C. Byrd, Daniel H. Ess, Robert S. Paton, Corey R. J. Stephenson
Summary: Cuneane, a strained hydrocarbon, can be accessed via metal-catalyzed isomerization of cubane. It has a polyhedral structure with six faces of different shapes. The rigidity and unique properties make it a potential scaffold for the synthesis of small molecules and materials. However, previous synthetic efforts have been limited to monosubstituted or redundantly substituted cuneanes, and more complex substitution patterns are needed for the study of this ring system in various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Calum Patel, Emy Andre-Joyaux, Jamie A. Leitch, Xabier Martinez de Irujo-Labalde, Francesco Ibba, Job Struijs, Mathias A. Ellwanger, Robert Paton, Duncan L. Browne, Gabriele Pupo, Simon Aldridge, Michael A. Hayward, Veronique Gouverneur
Summary: This article introduces a method of reacting acid-grade fluorspar with dipotassium hydrogen phosphate under mechanochemical conditions, resulting in a solid product suitable for forming sulfur-fluorine and carbon-fluorine bonds.
Article
Chemistry, Multidisciplinary
S. V. Shree Sowndarya, Yeonjoon Kim, Seonah Kim, Peter C. St. John, Robert S. Paton
Summary: This study advances the accuracy and applicability of machine learning in predicting bond dissociation energy by expanding and updating the model. The new model includes more elements and bond types, and successfully improves predictive accuracy by introducing more training data, which is of great significance for the application of molecules in medicine and the environment.
Article
Computer Science, Artificial Intelligence
Shree S. Sowndarya, Jeffrey N. Law, Charles E. Tripp, Dmitry Duplyakin, Erotokritos Skordilis, David Biagioni, Robert S. Paton, Peter C. St John
Summary: Advances in goal-directed molecular optimization provide hope for finding feasible candidates for challenging molecular design applications. In this study, a new open-source molecular optimization framework based on AlphaZero coupled with machine learning and quantum chemistry simulations was developed to find stable radical compounds that satisfy redox and stability requirements.
NATURE MACHINE INTELLIGENCE
(2022)