Review
Chemistry, Multidisciplinary
Gianluigi Albano, Angela Punzi, Maria Annunziata M. Capozzi, Gianluca M. Farinola
Summary: This review offers a critical overview of the research on sustainable strategies for direct C-H bond arylation of (hetero)arenes, focusing on recoverable catalysts, sustainable solvents, and non-conventional energy sources.
Article
Chemistry, Physical
Xianglin Luo, Zhewei Li, Yuzhen Zheng, Yueping Lin, Huanfeng Jiang, Lukas J. Goossen, Ming Lei, Liangbin Huang
Summary: Directed C-H arylations are widely used strategies for the synthesis of biaryls. However, their sensitivity to steric hindrance is a limitation. In this study, a ruthenium catalyst is used to overcome this limitation and achieve high yields of ortho-C-H arylation. The combination of a carboxylate directing group and chelating N-ligand is found to be crucial for the selectivity of the reaction.
Article
Chemistry, Organic
Alexis L. Gabbey, Nicholas W. M. Michel, Jonathan M. E. Hughes, Louis-Charles Campeau, Sophie A. L. Rousseaux
Summary: In this study, a new strategy was reported for the synthesis of secondary α-aryl amides through a nickel-catalyzed reductive arylation reaction using N-hydroxyphthalimide (NHP) esters of malonic acid half amides as redox-active substrates. This method proceeds under mild conditions and exhibits excellent chemoselectivity for amide α-arylation in the presence of other enolizable carbonyls.
Article
Chemistry, Multidisciplinary
Dake Song, Yi Qin, Ying Liu, Jifan Wang, Haijie Yang, Zhonghui Zheng, Feng Xu, Xuefei Bao, Guoliang Chen
Summary: The immobilization of ciprofloxacin on chloromethyl polystyrene resin as a recyclable ligand for copper-catalyzed coupling reactions of (hetero)aryl halides and amines provides excellent results. The ligand is easily recovered and reused without loss of catalytic ability, and is environmentally friendly with no detectable ciprofloxacin in the reaction solution. Important structural units for the pharmaceutical and chemical industries can be assembled using this method.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Kartic Manna, Ranjan Jana
Summary: We describe a mild and highly selective palladium-catalyzed cross-electrophile coupling between aromatic diazonium salts and aryl iodides or diaryliodonium salts in a water-ethanol (2:1) medium. Mechanistic studies revealed the importance of ethanol in generating an active Pd(0) catalyst, and the counterion of the diazonium salt promotes the formation of a cationic Pd(II) species that facilitates subsequent oxidative addition to aryl iodides/diaryliodonium salts. The presence of silver(I) salt is crucial for maintaining the catalytic activity of palladium by removing iodide ions as precipitates.
Article
Chemistry, Organic
An-Di Liu, Zhao-Li Wang, Li Liu, Liang Cheng
Summary: The direct C5 (hetero)arylation of uracil and uridine substrates with (hetero)aryl diazonium salts under photoredox catalysis with blue light was reported. The coupling proceeds efficiently with good functional group tolerance at room temperature in aqueous solution without transition-metal components. A plausible radical mechanism has been proposed for this reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Bokka Srinivas, Kotari Shakeena, Durgeswari Lakkavarapu Kota, Valeti Abhinav, Pyla Eswar, Rongali Geetha Sravani, Anandam Sampath Pavan Kumar, Kiran Indukuri, Kumpatla Ayyappa Dhanaraju, Muthyala Murali Krishna Kumar, Santhosh Kumar Alla
Summary: A direct synthetic route for the preparation of 2-arylbenzothiazoles using aryl isothiocyanates and electron-rich arenes is reported. The route involves triflic acid promoted addition of the arenes to aryl isothiocyanates followed by FeCl3-catalyzed C-S bond formation via C-H functionalization. This approach offers the advantage of synthesizing benzothiazoles without the need for expensive aryl aldehyde/carboxylic acid precursors.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Gajanan K. Rathod, Rahul Jain
Summary: We report the palladium-catalyzed aminocarbonylation of (hetero)aryl iodides using alpha-amino acid esters as nucleophiles. The synthesized N-capped alpha-amino acids are important building blocks in biology. The reaction is carried out under mild conditions, yielding products with high enantioselectivity in a short period of time. Additionally, regioselective carbonylation of histidine is achieved for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Li-Chen Xu, Xiao-Di Ma, Kun-Ming Liu, Xin-Fang Duan
Summary: In this study, a new method is proposed to achieve regioselective alkylation of pyridines at the C2 position, providing an important synthetic tool for late-stage diversification of drugs.
Article
Chemistry, Multidisciplinary
Travis J. DeLano, Sara E. Dibrell, Caitlin R. Lacker, Adam R. Pancoast, Kelsey E. Poremba, Leah Cleary, Matthew S. Sigman, Sarah E. Reisman
Summary: The study reports an asymmetric reductive cross-coupling reaction with good enantioselectivity using nickel-catalysis and a chiral BiOX ligand to synthesize alpha-arylesters under mild conditions. The reaction shows good yields and enantioselectivities, tolerates a wide range of functional groups, and the resulting products can be used to prepare pharmaceutically-relevant chiral building blocks. Additionally, a multivariate linear regression model was developed to quantify the influence of the alpha-chloroester substrate and ligand on enantioselectivity.
Review
Chemistry, Organic
Renzo Rossi, Maurizio Ciofalo
Summary: This review gives a comprehensive overview of the Pd-catalysed intermolecular direct C-H bond arylation of heteroarenes with arylating reagents. It summarizes the preparation of various arylating reagents, evaluates the practicality, versatility, and limitations of the arylation protocols, and compares the results with reactions using aryl halides as electrophiles. Mechanistic proposals are also discussed.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chongyang Wu, Tao Ying, Xinjie Yang, Weike Su, Alexandr V. Dushkin, Jingbo Yu
Summary: A novel method for synthesizing 4-alkylpyrimidines through mechanochemical magnesium-mediated Minisci reaction has been reported. The process shows broad substrate scope and excellent regioselectivity under mild conditions without the need for transition-metal catalysts, solvents, and inert gas protection. The practicality of this protocol has been demonstrated through up-scale synthesis, mechanochemical product derivatization, and preparation of the antimalarial drug pyrimethamine.
Article
Chemistry, Organic
Ting Cui, Yanling Zhan, Changhui Dai, Jun Lin, Ping Liu, Peipei Sun
Summary: An electrochemical oxidative regioselective C-H cyanation of imidazo[1,2-a]pyridines was developed utilizing TMSCN as the cyano source, with the KH2PO4/K2HPO4 buffer being essential for the transformation. This protocol was compatible with a broad range of substituted imidazo[1,2-a]pyridines and provided the C3 cyanated products in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yue Zhao, Congjun Yu, Wenjing Liang, Frederic W. Patureau
Summary: The construction of (hetero)biaryls through a photoinduced and catalyst-free C-H/C-H cross-coupling provides a simple and efficient synthetic approach by selectively forming aryl thianthrenium salts. Using UV-light to disrupt the C-S bond allows for the formation of thianthrene radical cations and aryl radicals.
Article
Chemistry, Multidisciplinary
Xia Hu, Ivan Cheng-Sanchez, Sergio Cuesta-Galisteo, Cristina Nevado
Summary: An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling reaction was developed for the synthesis of enantioenriched beta-aryl homoallylic amines with excellent E-selectivity. This reaction proceeds under mild conditions without the use of heterogeneous metal reductants and sacrificial anodes, employing constant current electrolysis with triethylamine as a terminal reductant. The reaction demonstrates remarkable stereocontrol, broad substrate scope, and excellent functional group compatibility, making it suitable for the late-stage modification of bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Davide Dova, Silvia Cauteruccio, Norberto Manfredi, Stefan Prager, Andreas Dreuw, Serena Arnaboldi, Patrizia R. Mussini, Emanuela Licandro, Alessandro Abbott
Article
Biochemistry & Molecular Biology
Silvia Mercurio, Silvia Cauteruccio, Raoul Manenti, Simona Candiani, Giorgio Scari, Emanuela Licandro, Roberta Pennati
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2020)
Article
Chemistry, Physical
Tommaso Taroni, Silvia Cauteruccio, Riccardo Vago, Stefano Franchi, Nadia Barbero, Emanuela Licandro, Silvia Ardizzone, Daniela Meroni
APPLIED SURFACE SCIENCE
(2020)
Article
Chemistry, Organic
Valentina Pelliccioli, Giuseppe Dilauro, Sara Grecchi, Serena Arnaboldi, Claudia Graiff, Filippo M. Perna, Paola Vitale, Emanuela Licandro, Alessandro Aliprandi, Silvia Cauteruccio, Vito Capriati
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Pharmacology & Pharmacy
Pramod Thakare, Francesca Vasile, Maura Vallaro, Sonja Visentin, Giulia Caron, Emanuela Licandro, Silvia Cauteruccio
Summary: The first comprehensive study on the ionization and lipophilic properties of peptide nucleic acid (PNA) derivatives was conducted, revealing that single nucleobases do not alter their pKa values when incorporated into PNA monomers and oligomers. Additionally, the PNA derivatives showed poor affinity towards membrane phospholipids and limited cell penetrating ability. The study has potential implications for evaluating the pharmacokinetic properties of PNA and for enhancing cell penetration properties through proper modification.
JOURNAL OF PHARMACEUTICAL ANALYSIS
(2021)
Article
Materials Science, Multidisciplinary
Alberto Bossi, Serena Arnaboldi, Carlo Castellano, Rocco Martinazzo, Silvia Cauteruccio
ADVANCED OPTICAL MATERIALS
(2020)
Article
Chemistry, Organic
Valentina Pelliccioli, Davide Dova, Clara Baldoli, Claudia Graiff, Emanuela Licandro, Silvia Cauteruccio
Summary: Efficient and versatile synthetic routes to functionalized tetrathia[7]helicenes (7-THs) have been described in this study. Key intermediates were synthesized using palladium-catalyzed homocoupling reactions and annulation reactions. The versatility of bromides 1 for preparing a variety of 7-TH derivatives, including 7,8-disubstituted and 7-monosubstituted compounds, has been demonstrated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Valentina Pelliccioli, Thierry Hartung, Martin Simon, Christopher Golz, Emanuela Licandro, Silvia Cauteruccio, Manuel Alcarazo
Summary: The study reports a highly enantioselective synthesis of 5,13-disubstituted dibenzo[d,d']benzo[1,2-b:4,3-b']dithiophenes, with the last two successive Au-catalyzed intra-molecular alkyne hydroarylation events being crucial for the successful assembly of these helical architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Valentina Pelliccioli, Francesca Cardano, Giacomo Renno, Francesca Vasile, Claudia Graiff, Giuseppe Mazzeo, Andrea Fin, Giovanna Longhi, Sergio Abbate, Alessia Rosetti, Claudio Villani, Guido Viscardi, Emanuela Licandro, Silvia Cauteruccio
Summary: This study reports the synthesis of a novel class of functionalized thia[6]helicenes and a thia[5]helicene, and investigates their configurational stability and photophysical properties. Experimental and theoretical studies confirmed the stability of selected thia[6]helicenes, while the pyrene-based thia[5]helicene was found to be unstable. The configuration assignment for one representative thiahelicene was established through the comparison between experimental and theoretical circular dichroism (CD) spectra.
Article
Chemistry, Organic
Nicolas D'Imperio, Valentina Pelliccioli, Sara Grecchi, Alberto Bossi, Francesca Vasile, Silvia Cauteruccio, Anna I. Arkhypchuk, Arvind Kumar Gupta, Andreas Orthaber, Sascha Ott, Emanuela Licandro
Summary: This paper describes the first examples of a pi-conjugated benzo[b]phosphole P-oxide, in which two phosphole P-oxide units are connected by a carbon-carbon double bond. The molecules exist as stable cis and trans isomers (chiral and meso one respectively) with respect to the two stereogenic P atoms. The optical and electrochemical properties of both isomers have been investigated through experiments and computations.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alberto Bossi, Patrizia R. Mussini, Gianluca Farinola, Marta Penconi, Silvia Cauteruccio, Mark E. Thompson, Emanuela Licandro
Summary: In the thiahelicene family, selecting fluorine-containing groups can overcome the issue of structure-property correlations, and fluorine-functionalized tetrathia[7]helicenes were found to display green phosphorescence and efficient spin-orbit coupling mechanism in high-energy triplet nonplanar conjugated molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
Materials Science, Biomaterials
Serena Riela, Ana Borrego-Sanchez, Silvia Cauteruccio, Raquel de Melo Barbosa, Marina Massaro, C. Ignacio Sainz-Diaz, Rita Sanchez-Espejo, Cesar Viseras-Iborra, Emanuela Licandro
Summary: This study systematically investigates the interaction between three differently charged PNAs and halloysite. Understanding the interaction mode between charged molecules and clay surfaces is crucial for the design and development of halloysite-based materials for the delivery and release of PNAs. The results show that PNAs interact with halloysite surfaces in different ways according to their charge, which affects their release in physiological conditions.
JOURNAL OF MATERIALS CHEMISTRY B
(2023)
Article
Chemistry, Multidisciplinary
Valentina Pelliccioli, Roberta Franzini, Giuseppe Mazzeo, Claudio Villani, Sergio Abbate, Giovanna Longhi, Emanuela Licandro, Silvia Cauteruccio
Summary: This study investigated the stereochemical and chiroptical properties of a series of axially chiral intermediates, showing potential for developing chiral systems applicable in asymmetric synthesis, catalysis, and materials chemistry.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Serena Arnaboldi, Silvia Cauteruccio, Sara Grecchi, Tiziana Benincori, Massimo Marcaccio, Alessio Orbelli Biroli, Giovanna Longhi, Emanuela Licandro, Patrizia Romana Mussini
