Article
Chemistry, Multidisciplinary
Jianyang Dong, Andreas Ostertag, Christof Sparr
Summary: In this study, the accessibility of atropisomeric o-quinodimethanes and the enantioselective synthesis of their precursors were described. The catalyst-stereocontrolled [2+2+2] cycloaddition and subsequent stereospecific Diels-Alder reactions enabled the synthesis of enantioselective compounds with high selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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.
Article
Chemistry, Organic
Wynter E. G. Osminski, Zhenjie Lu, Wenjun Zhao, Aliakbar Mohammadlou, Xiaopeng Yin, Emily C. Matthews, Virginia M. Canestraight, Richard J. Staples, Connor J. Allen, Jennifer S. Hirschi, William D. Wulff
Summary: Boroxinate complexes of VAPOL and VANOL serve as a versatile staging arena for asymmetric catalysis, where multiple chiral catalysts can be rapidly assembled from various alcohols and bis-phenol ligands for screening of catalyst activity. The effect of variations in the steric and electronic properties of the phenol/alcohol component of the boroxinate catalyst on asymmetric induction in catalytic reactions is explored in this study. The mechanism of the boroxinate catalyst in catalytic asymmetric aziridination reaction involves hydrogen bonding to the boroxinate core rather than functioning as a Lewis acid.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Aluru Rammohan, Alexey P. Krinochkin, Albert F. Khasanov, Dmitry S. Kopchuk, Grigory Zyryanov
Summary: This review summarizes the applications of Diels-Alder reactions in the synthesis of heterocyclic compounds and materials without solvents, including mechanochemical grinding, catalysis, thermal, and electromagnetic radiation. The review validates the importance of Diels-Alder reactions in pharmaceutical innovation and biorenewable materials.
TOPICS IN CURRENT CHEMISTRY
(2022)
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
Chemistry, Organic
Hongling Wang, Qiangqiang Zhang, Shuai Xiao, Guanjie Wang, Xuan Huang, Xingkuan Chen, Junmin Zhang
Summary: We have developed a N-heterocyclic carbene (NHC) and base-mediated [3 + 3] annulation reaction for the synthesis of enantioselective dihydropyrano[3,2-b]indoles. Easily prepared sulfonium salts were used as precursors and reacted with unsaturated acyl azolium to achieve this transformation. The reaction conditions are mild and result in privileged indole-fused dihydropyranones with moderate to good yields and excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Sloan Ayers, Gregory L. Beutner, Wei Ding, Carolyn Higman, Charles Pathirana, Robert Wethman
Summary: Having reliable methods to monitor catalyst activation processes is crucial for ensuring the reproducibility of catalytic reactions. For asymmetric Diels-Alder reactions, chiral oxazaborolidine or oxazaborolidinium catalysts are powerful reagents that promote these reactions with high yield and selectivity. By investigating the mechanism, several modern analytical methods are compared to quantitate the formation of oxazaborolidine catalyst from amino alcohol and boroxine, leading to useful monitoring methods for this important transformation.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Huy Tran, Guillaume Revol, Alyson Poyser, Louis Barriault
Summary: In this study, a novel Lewis acid gold catalyst was used to generate synthetically challenging polycyclic scaffolds through a one-pot cascade sequence. By controlling the ligand and reaction conditions, both 6,6,5-tricyclic and 6,6,6,5-tetracyclic cores were selectively synthesized in one operation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Han-Han Kong, Cuiju Zhu, Shuang Deng, Guang Xu, Ruinan Zhao, Chaochao Yao, Hua-Ming Xiang, Chunhui Zhao, Xiaotian Qi, Hao Xu
Summary: The copper-catalyzed enantioselective [4 + 1] annulation of yne-allylic esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy, leading to the formation of diverse spirocycles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Wei-Ling Jiang, Bin Huang, Meng-Xiang Wu, Ye-Kai Zhu, Xiao-Li Zhao, Xueliang Shi, Hai-Bo Yang
Summary: The preparation of stable MOFs with organic radicals is challenging due to the reactivity of most organic radicals. A novel MOF containing phenazine radical cations was successfully synthesized using a post-synthetic modification strategy. The resulting MOF demonstrated high catalytic activity in aza-Diels-Alder reactions and excellent stability and recyclability, suggesting the potential of the developed strategy for preparing radical-based MOFs for heterogeneous catalysis in organic synthesis.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Razvan C. Cioc, Marc Crockatt, Jan C. van Der Waal, Pieter C. A. Bruijnincx
Summary: A hydrazine-mediated approach was used to produce renewable aromatics by Diels-Alder aromatization of biobased furfurals. The synthesis of aromatics using this method was selective, simple, and mild.
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
Chemistry, Multidisciplinary
Casper L. Barlose, Niklas L. ostergaard, Rene S. Bitsch, Marc V. Iversen, Karl Anker Jorgensen
Summary: An enantioselective methodology for constructing trans-Diels-Alder scaffolds with up to five contiguous stereocenters is presented, utilizing a halogen effect and a novel discovered pseudo-halogen effect. The reaction involves an endo-selective, secondary-amine catalyzed Diels-Alder reaction followed by a subsequent S(N)2-like reaction at a tertiary center to obtain the trans-Diels-Alder scaffold. The mechanism was supported by experimental results and computational studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jan Faehrmann, Gerhard Hilt
Summary: The study presents the acyl nitroso Diels-Alder reaction of 1,3-dienes with electrochemically oxidised hydroxamic acids. By utilizing alternating current electrolysis and optimizing the reaction conditions through Design of Experiments, high purity products were obtained with yields up to 96%, without the need for further purification.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Jie Yan, Marta Krasowska, Wei Ge, Kirsten Platts, Paula Facal Marina, Anton Blencowe
Summary: Injectable hydrogels with tuneable properties were developed for sustained drug delivery. These hydrogels can be easily processed at ambient temperature, and rapidly gel at physiological temperature to limit burst release of their payload.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Multidisciplinary Sciences
Jeroen B. I. Sap, Claudio F. Meyer, Joseph Ford, Natan J. W. Straathof, Alexander B. Durr, Mariah J. Lelos, Stephen J. Paisey, Tim A. Mollner, Sandrine M. Hell, Andres A. Trabanco, Christophe Genicot, Christopher W. Am Ende, Robert S. Paton, Matthew Tredwell, Veronique Gouverneur
Summary: This study introduces a novel [F-18] difluorocarbene reagent, which resolves the issue of high molar activity in F-18 difluoromethylated molecules by incorporating carbene chemistry, showcasing its versatility and ease of access.
Article
Chemistry, Multidisciplinary
Roman Belle, Jos J. A. G. Kamps, Jordi Poater, Kiran Kumar, Bas J. G. E. Pieters, Eidarus Salah, Timothy D. W. Claridge, Robert S. Paton, F. Matthias Bickelhaupt, Akane Kawamura, Christopher J. Schofield, Jasmin Mecinovic
Summary: The substitution of nitrogen with phosphorus substantially affects the interactions between N-epsilon-methyllysine binding proteins and demethylases.
COMMUNICATIONS CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Sudip Maiti, Yingzi Li, Sheuli Sasmal, Srimanta Guin, Trisha Bhattacharya, Goutam Kumar Lahiri, Robert S. Paton, Debabrata Maiti
Summary: In this study, a robust method for para-C-H arylation of arenes, including bioactive molecules, has been developed. The method allows the synthesis of therapeutics with high affinity and specificity for protein targets.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Katie Ruffell, Liliana C. Gallegos, Kenneth B. Ling, Robert S. Paton, Liam T. Ball
Summary: This study demonstrates the utility of a modular, bismacycle-based system for the O-selective arylation of 2- and 4-pyridones with arylboronic acids. The research also shows that the kinetically-controlled regioselectivity for O-arylation is attributed to the geometric constraints imposed by the bismacyclic scaffold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Meire Y. Kawamura, Juan Alegre-Requena, Thais M. Barbosa, Claudio F. Tormena, Robert S. Paton, Marco A. B. Ferreira
Summary: [3+2] cycloadditions of nitroolefins are a selective and catalyst-free alternative for synthesizing 1,2,3-triazoles. Mechanistic studies reveal that the rate-limiting step is the cycloaddition, which shows high kinetic selectivity for the formation of 1,5-triazoles.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Correction
Multidisciplinary Sciences
Sudip Maiti, Yingzi Li, Sheuli Sasmal, Srimanta Guin, Trisha Bhattacharya, Goutam Kumar Lahiri, Robert S. Paton, Debabrata Maiti
NATURE COMMUNICATIONS
(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
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.
