Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Applied
Liam Byrne, Christian Skold, Per-Ola Norrby, Rachel H. Munday, Andrew R. Turner, Peter D. Smith
Summary: The development of biaryl 2,5-diphenylphospholanes as a new class of C-2-symmetric, monodentate ligands for asymmetric Suzuki-Miyaura (ASM) reactions has led to the successful preparation of a range of atropisomeric biaryl and heterobiaryl products with good to excellent levels of enantioselectivity. DFT studies indicate that the formation of a constraining ligand pocket and coordination of one of the biaryl methoxy groups to the metal center in the optimized ligands are crucial for restricting conformational freedom in the bond-forming step.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Julius Hoepfner, Marius Brehm, Pavel A. Levkin
Summary: The rising costs of pharmaceutical research are currently limiting the productivity of drug discovery and development, but can potentially be reduced through miniaturization of compound synthesis and screening. In this study, the influential palladium-catalyzed Suzuki-Miyaura reaction is successfully implemented at the nanoliter scale on droplet microarrays for the synthesis of an 800-compound library of biphenyls. The synthesis of these compounds requires minimal reagents and solvent volume, and the obtained compounds can be purified and cleaved from excess reactants and catalyst. This novel approach expands the capabilities of droplet microarrays for miniaturized high-throughput chemical synthesis and opens up possibilities for future synthesis and screening of chemical compounds in a single platform.
Article
Chemistry, Physical
Raquel dos Santos, Vitor Hugo M. Vitoi, Marcio Costa, Lorenna C. L. L. F. da Silva, Braulio S. Archanjo, Carlos A. Achete, Raphael S. F. Silva, Lucia C. S. Aguiar, Luiz Fernando B. Malta, Jaqueline D. Senra
Summary: Corn-starch was used to reduce Pd(II) species and form a thermoresponsive palladium nanoparticles-containing hydrogel with an average size of 16.1 nm +/- 6.4 nm. It was successfully applied in a Suzuki-Miyaura reaction in water for the synthesis of a precursor of an unnatural quaternary biarylalanine.
Article
Chemistry, Multidisciplinary
Qian Shang, Haifang Tang, Yongping Liu, Mingming Yin, Lebin Su, Shimin Xie, Lixin Liu, Wen Yang, Yi Chen, Jianyu Dong, Yongbo Zhou, Shuang-Feng Yin
Summary: The selective condensation/bicycloaromatization of two different arylalkynes was achieved under ligand-free copper (I) catalysis, allowing for the direct synthesis of C-N axial biaryl compounds in high yields with excellent selectivity and functional group tolerance. The use of Cu (I) catalyst and HFIP played critical roles in suppressing undesired reactions and constructing coupled five-six aromatic rings through the selective formation of C(sp(2))-N(sp(2)) bonds and C(sp(2))-C(sp(2)) bonds. This unique reaction has the potential to lead to the simplest asymmetric synthesis of atropoisomeric biaryls, with promising applications in various fields such as biology and pharmaceuticals.
Article
Chemistry, Applied
Kanticha Khomthawee, Nattaporn Nilada, Antika Homchuen, Pranorm Saejueng
Summary: The CS-EDTA-Pd catalyst was prepared by dissolving chitosan and EDTA in acetic acid, forming beads, adsorbing palladium(II), and reducing it to palladium(0) with ethanol reflux. The catalyst was characterized by various techniques. It was then tested in the Suzuki-Miyaura cross-coupling reaction and showed good catalytic activity. The catalyst is inexpensive, easy to prepare, and can be reused multiple times with only a slight loss in product yields.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhenzhong Zhang, Aya Ohno, Hikaru Takaya, Yoichi M. A. Yamada
Summary: Researchers developed a catalyst for Suzuki-Miyaura coupling under flow conditions using a molecular convolution method. The catalyst showed high performance and durability, allowing for the continuous synthesis of two pharmaceuticals in water as the sole solvent.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Angus Olding, Curtis C. Ho, Allan J. Canty, Nigel T. Lucas, James Horne, Alex C. Bissember
Summary: This study reports the synthesis of a family of unprecedented arylpalladium(II) boronates that are kinetically stable at ambient temperature, and their chemical competence in a Suzuki-Miyaura reaction was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sheng-Qi Qiu, Yu Chen, Xiang-Jun Peng, Shi-Jiang He, Jun Kee Cheng, Yong-Bin Wang, Shao-Hua Xiang, Jun Song, Peiyuan Yu, Junmin Zhang, Bin Tan
Summary: In this study, we achieved the arene-alkene Suzuki-Miyaura coupling reaction between hindered aryl halides and vinyl boronates by designing appropriate ligands and reaction parameters. The axially chiral acyclic aryl-alkenes obtained exhibited remarkable efficiency, enantioselectivity, and E/Z selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Noelia Esteban, Miguel Claros, Cristina Alvarez, Angel E. Lozano, Camino Bartolome, Jesus M. Martinez-Ilarduya, Jesus A. Miguel
Summary: A new set of microporous organic polymers (POPs) with high microporosity and moderate thermal stability has been synthesized via Friedel-Crafts knitting. These polymers, containing diphosphine derivatives, act as efficient catalysts for Suzuki-Miyaura coupling reactions, exhibiting excellent recyclability.
Article
Chemistry, Multidisciplinary
Matteo Albino, Thomas J. Burden, Carmen C. Piras, Adrian C. Whitwood, Ian J. S. Fairlamb, David K. Smith
Summary: The increase in demand and low abundance of palladium pose a significant threat to its future availability, making research into sustainable palladium-based technologies crucial. This study reports the development of Pd scavenging hybrid gel beads composed of agarose and a low-molecular-weight gelator based on DBS-CONHNH2. These mechanically robust gel beads exhibit potential as practical catalysts for Suzuki-Miyaura cross-coupling reactions, demonstrating good reusability, green metrics, and improved reaction times compared to previous examples. The leaching of palladium is almost completely eliminated and a detailed investigation explains how the nanoparticles are formed in situ. These ligand-free gel beads can be considered as robust nonligated heterogeneous PdNP catalysts with potential for the development of easily used chemical reaction systems.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Antonio J. LaPorte, Yao Shi, Jason E. Hein, Martin D. Burke
Summary: Stereospecific Csp(3) Suzuki-Miyaura cross-coupling simplifies the synthesis of stereochemically complex small molecules, but current methods are not compatible with complex building blocks commonly found in natural products and other complex targets. This study presents a method for embedding the alpha-methyl-beta-hydroxyl motif within stereochemically defined secondary alkyl boronic ester building blocks, allowing for stereospecific cross-coupling. The use of beta-aryloxysilyl groups addresses the decrease in reactivity and side reactions associated with beta-oxygen-containing Csp(3) boronic esters. Mechanistic studies reveal the activation of a dihydroxysiloxaborolate as a transmetalation partner in a stereospecific process that retains configuration.
Article
Chemistry, Physical
Chau Ming So, On Ying Yuen, Shan Shan Ng, Zicong Chen
Summary: This study presents a general chemoselective Suzuki-Miyaura coupling using a Pd/L33 catalyst, showing efficient coupling of polyhalogenated aryl triflates by controlling reactivity order and key factors, achieving high yields and chemoselectivity with low Pd catalyst loading.
Article
Multidisciplinary Sciences
Kai Yang, Yanfei Mao, Zhihan Zhang, Jie Xu, Hao Wang, Yong He, Peiyuan Yu, Qiuling Song
Summary: The authors report a tetracoordinate boron-directed dynamic kinetic asymmetric transformation (DyKAT) method for the construction of C-B axial chirality using racemic, configurationally stable 3-bromo-2,1-azaborines. By rational design of a reversible tetracoordinate boron intermediate, a series of challenging C-B axially chiral compounds were prepared with generally good to excellent enantioselectivities. This method can also be extended to prepare atropisomers bearing adjacent C-B and C-C diaxes with excellent diastereo- and enantio-control.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Karan Goswami, Dipak Das, Parthasarathi Bera, Sounak Roy, Md. Motin Seikh, Prasanta Kumar Sinha, Arup Gayen
Summary: This work presents the development of a simple and highly active heterogeneous Pd catalyst for Suzuki-Miyaura carbon-carbon cross-coupling reaction. The NiPdFe-1 catalyst shows the best activity and stability among the prepared catalysts. It efficiently promotes the coupling reaction between aryl bromide and phenyl boronic acid under mild reaction conditions with high isolated yields.
JOURNAL OF MOLECULAR STRUCTURE
(2024)
Article
Chemistry, Analytical
Chiara Cantatore, Paola Bertocchi, Daniela De Orsi, Alessia Panusa, Roberto Cirilli
Summary: Normal-phase and reversed-phase high-performance liquid chromatography methods were developed to separate the active pharmaceutical ingredient escitalopram from its (R)-enantiomer impurity. Both methods used ethanol as a cosolvent and achieved complete enantioseparation without interference from other associated chiral impurities.
JOURNAL OF SEPARATION SCIENCE
(2022)
Article
Infectious Diseases
Massimiliano De Angelis, Maria T. Mascellino, Maria C. Miele, Dania Al Ismail, Marisa Colone, Annarita Stringaro, Vincenzo Vullo, Mario Venditti, Claudio M. Mastroianni, Alessandra Oliva
Summary: This study aimed to evaluate the in vitro activity of N-acetylcysteine (NAC) alone or in combination with beta-lactams against carbapenem-resistant Klebsiella pneumoniae (CR-Kp) and Acinetobacter baumannii (CR-Ab). The results showed that NAC had high in vitro activity against CR-Kp and CR-Ab and enhanced the susceptibility of beta-lactams in the tested strains.
Article
Infectious Diseases
Alberto Vitali, Annarita Stringaro, Marisa Colone, Alexandra Muntiu, Letizia Angiolella
Summary: Chitosan nanoparticles loaded with carvacrol showed strong antifungal activity against planktonic Candida strains, and the antibiofilm activity varied depending on the species tested.
Article
Microbiology
Francesca Mondello, Stefano Fontana, Maria Scaturro, Antonietta Girolamo, Marisa Colone, Annarita Stringaro, Maura Di Vito, Maria Luisa Ricci
Summary: This study evaluated the in vitro activity of Terpinen-4-ol as a potential agent for Legionella pneumophila (Lp) control and compared it with tea tree oil. The results showed that Terpinen-4-ol exhibited strong antimicrobial activity against Lp, with enhanced bactericidal effects at higher temperatures.
Article
Chemistry, Medicinal
Gerardo Salinas, Filippo Malacarne, Giorgia Bonetti, Roberto Cirilli, Tiziana Benincori, Serena Arnaboldi, Alexander Kuhn
Summary: A microfluidic valve based on chemically responsive materials is reported, which is triggered by bipolar electrochemistry and chiral recognition. The valve can be opened and closed by reversible deflection of a conducting polymer actuator, allowing the release of dye from a reservoir. The device works well even in the presence of chemically different chiral analytes in the same solution, opening up new possibilities in microfluidics, including controlled drug delivery applications.
Review
Biochemistry & Molecular Biology
Claudio Tabolacci, Daniela De Vita, Antonio Facchiano, Giuseppina Bozzuto, Simone Beninati, Cristina Maria Failla, Marta Di Martile, Carla Lintas, Carlo Mischiati, Annarita Stringaro, Donatella Del Bufalo, Francesco Facchiano
Summary: Improving the immune response is important for treating melanoma, and plant secondary metabolites have been considered as potentially useful therapeutic tools due to their low side effects and high effectiveness. This study reviews the current research on the topic, which mainly focuses on conducting in vitro and in vivo experiments on melanoma models.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Francesca Romana Mammone, Leo Zanitti, Michela Puxeddu, Giuseppe La Regina, Romano Silvestri, Anna Borioni, Roberto Cirilli
Summary: A direct and highly selective ultra-high-performance liquid chromatographic method was developed and validated for determining the content of rosuvastatin calcium salt (RSV) in medicinal products. The method achieved baseline separation of all organic related substances listed in the European Pharmacopoeia monograph for RSV tablets in less than 15 minutes. The method was proven to be linear, precise, and accurate for determining RSV and related chiral substances in tablet formulations according to the guidelines of the International Conference on Harmonization (ICH).
Article
Chemistry, Multidisciplinary
Alessia Rosetti, Giulio Apolloni, Claudio Villani, Tiziana Benincori, Roberto Cirilli
Summary: In this study, a new atropisomeric C-2-symmetry chiral monomer based on the 3,3'-bithiophene core was synthesized and resolved by high-performance liquid chromatography (HPLC). The enantioseparation was optimized using a cellulose-type Chiralpak IB-3 column and a specific mobile phase. Scale-up of the enantioseparation process led to notable deformations in the HPLC profile, which were investigated and addressed. The optimized chromatographic conditions were then used to obtain milligram amounts of enantiopure sample for further characterization studies.
APPLIED SCIENCES-BASEL
(2023)
Article
Biochemistry & Molecular Biology
Giuseppina Bozzuto, Marisa Colone, Laura Toccacieli, Agnese Molinari, Annarica Calcabrini, Annarita Stringaro
Summary: In this study, the mechanisms of melanoma cell extravasation were analyzed using a high throughput label-free cell impedance assay and transwell chamber invasion assay. The results showed that resistant melanoma cells migrated faster than sensitive cells, and caused damage to endothelial cells by degrading their cytoplasm. Moreover, the transcellular invasion was preferred by resistant cells compared to the paracellular one, and the endothelial damage mediated by tumor metalloproteinases seemed to be reversible.
Article
Chemistry, Analytical
Silvia Cauteruccio, Valentina Pelliccioli, Sara Grecchi, Roberto Cirilli, Emanuela Licandro, Serena Arnaboldi
Summary: In this study, a wireless miniaturized stereoselective light-emitting system was designed to qualitatively detect chiral contaminants in reduced volumes. By mixing an inherently chiral inductor with a chiral probe in micro-solutions of a commercial ionic liquid, an asymmetric environment was created. The synergy between the inductor, the applied electric field, and the chiral pollutant was transduced by the light emission produced from a miniaturized light-emitting diode (LED) used as a bipolar electrode.
Article
Chemistry, Organic
Fabio Buonsenso, Marta Colombo, Andrea Marchesi, Francesca Romana Mammone, Francesco Sannicolo, Roberto Cirilli, Marco Pierini
Summary: An experimental and theoretical study was conducted to analyze the configurational lability of drugs with a non-planar seven-membered cycloheptadiene ring, which confers chirality to these compounds. The study investigated the energy barrier opposing the inversion of the chiral tricyclic scaffold, which is dependent on appropriate substituents on the external cycles. Structural changes were made to accurately control the stereolability of the tricyclic framework, providing interesting insights.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Daniele Sadutto, Paolo Guglielmi, Simone Carradori, Daniela Secci, Roberto Cirilli
Summary: The study investigates the tautomerization process of the imine moiety of the isoxazoline ring in the presence of a basic catalyst. The results can be used to control the stereointegrity of pharmacologically active compounds and guide the synthesis towards the desired tautomer.
Article
Chemistry, Multidisciplinary
Simone Amatori, Alberto Lopez, Carlo Meneghini, Annarica Calcabrini, Marisa Colone, Annarita Stringaro, Sofia Migani, Ivan Khalakhan, Giovanna Iucci, Iole Venditti, Chiara Battocchio
Summary: Gold nanorods stabilized by binary ligand mixtures of CTAB and either ascorbic acid or hydroquinone were studied using synchrotron radiation-induced spectroscopies and microscopies. The influence of the secondary ligand molecular and chemical structure on the nanorod shapes and size ratios was investigated. The findings suggest that the selection of secondary ligands can finely control the shape and dimension of nanorods, providing new possibilities for designing and synthesizing anisotropic nanoparticles.
NANOSCALE ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
