Article
Chemistry, Organic
Zhongxue Fang, Yujie Zhang, Hongwei Wang, Giuseppe Zanoni, Jianxin Li, Xingqi Li, Zhaohong Liu, Yongquan Ning
Summary: A metal-free cycloaddition reaction of fluoroalkyl N-sulfonylhydrazones with arene-diazonium salts to form fluoroalkylated tetrazole products was reported. This procedure provides a general and safe method for accessing mono-, di-, and perfluoroalkyl tetrazoles with excellent yields and tolerance of diverse functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
David L. Cousins, Yee Hwee Lim, Joseph P. A. Harrity
Summary: We report a mild and regiospecific boron-directed benzannulation method for accessing a range of perfluoroalkyl-substituted (hetero)aromatic building blocks, which can be easily elaborated through established C-B bond functionalization processes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Anna Kubickova, Athanasios Markos, Svatava Voltrova, Anezka Markova, Josef Filgas, Blanka Klepetarova, Petr Slavicek, Petr Beier
Summary: N-Fluoroalkylated 1,2,3-triazoles undergo a microwave-heating-assisted ring opening, nitrogen molecule elimination, and concomitant group rearrangement to form isolable N-fluoroalkylketenimines. This reagent-free process exhibits a wide scope and high efficiency, providing a new route to unexplored N-fluoroalkyl compounds. Mechanistic and computational studies were employed to investigate the reaction mechanism. [2 + 2] cycloaddition of ketenimines with alkynes or alkenes yields novel cyclobutenimines and cyclobutanimines, respectively. Addition of oxygen, sulfur, and nitrogen nucleophiles to ketenimines gives rise to new N-fluoroalkyl imidates, thioimidates, and amidines.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Multidisciplinary Sciences
Linxuan Li, Xinyu Zhang, Yongquan Ning, Xiaolong Zhang, Binbin Liu, Zhansong Zhang, Paramasivam Sivaguru, Giuseppe Zanoni, Shuang Li, Edward A. Anderson, Xihe Bi
Summary: A carbene-initiated rearrangement strategy has been developed for the selective carbodefluorination of fluoroalkyl ketones, providing diverse alpha-fluorinated ketones. This strategy offers significant advances over existing stepwise strategies in terms of selectivity, efficiency, and functional group tolerance.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Balint Varga, Balazs L. Toth, Ferenc Beke, Janos T. Csenki, Andras Kotschy, Zoltan Novak
Summary: A novel fluoroalkyl iodide was synthesized from refrigerant gas HFO-1234yf as a cheap starting material in a simple and scalable process, demonstrating its applicability in a metal-free photocatalytic ATRA reaction to synthesize valuable fluoroalkylated vinyl iodides and its transformability in cross-coupling chemistry to obtain conjugated systems.
Article
Chemistry, Multidisciplinary
Takashi Koike
Summary: This article introduces the easy-to-handle, solid, and bench-stable fluoroalkyl sulfoximines as electron-accepting fluoroalkyl radical sources, which can generate fluoroalkyl radicals using strong one-electron injectors. Our group has developed photocatalytic radical di- and mono-fluoromethylation and alpha-monofluoroalkylation of olefins using these sulfoximines. Appropriate combinations of fluoroalkyl sulfoximines and photoredox catalysts for successful radical fluoroalkylation have been discussed in this personal account.
Article
Pharmacology & Pharmacy
Mengmeng Zheng, Chunpu Li, Mi Zhou, Ru Jia, Fengyu She, Lulu Wei, Feng Cheng, Qi Li, Jianfeng Cai, Yan Wang
Summary: The study developed an artificial antibody based on gamma-AApeptides, with small molecular weight, antibody-like properties, strong resistance to proteolysis, excellent binding affinity to HER2, effective inhibition of cell proliferation in vitro, suppression of tumor growth in vivo, and potential therapeutic applications for treating cancers.
ACTA PHARMACEUTICA SINICA B
(2021)
Article
Chemistry, Organic
Amelia Messara, Nicolas Vanthuyne, Patrick Diter, Mourad Elhabiri, Armen Panossian, Gilles Hanquet, Emmanuel Magnier, Frederic R. Leroux
Summary: The study achieved enantiomeric separation of aryl trifluoromethyl and difluoromethyl sulfoxides using chiral chromatography, followed by investigating the configurational stability of each set of enantiomers. The results showed good optical stability of these compounds at room temperature, with a shorter half-life observed for difluoromethyl sulfoxides. Additionally, the acidities of six aryl difluoromethyl sulfoxides were determined and showed significant differences compared to non-fluorinated analogues.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yi Liu, Ji Li, Yulu Zhou, Hanliang Zheng, Zhenlu Shen, Gangguo Zhu
Summary: In this study, a visible-light-induced cascade radical cyclization method was developed for the synthesis of decorated a-fluoroalkyl cycloalkanols. The fluorine effect was found to play a crucial role in this reaction, as supported by density functional theory calculations.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Wenxu Chang, Zizhen Lei, Yi Yang, Sibo Dai, Jiyao Feng, Jun Yang, Zhenhua Zhang
Summary: In this study, a palladium-catalyzed tandem reaction of azide with isonitrile and fluoroalkylsilane was developed to access N-functionalized C-fluoroalkyl amidines. This protocol allows for the synthesis of a broad range of N-sulphonyl, N-phosphoryl, N-acyl, N-aryl, C-CF3, C2F5, and CF2H amidines. The successful gram-scale synthesis and biological evaluation of Celebrex derivatives demonstrate the utility of this strategy.
Article
Chemistry, Organic
Zhongxue Fang, Yanmei Gong, Binbin Liu, Jin Zhang, Xinyue Han, Zhaohong Liu, Yongquan Ning
Summary: Herein, we report the pioneering Rh-catalyzed coupling reactions between a fluoroalkyl carbene and azides to access alpha-trifluoroethylated imines. Through the use of fluoroalkyl N-sulfonylhydrazones as fluoroalkyl diazo surrogates, two C-N bond formation products were obtained using TMSN3 as the N source. Additionally, the alpha-trifluoroethylated imine products were easily reduced to the corresponding N-trifluoroethylated anilines. Experimental results and theoretical calculations support a stepwise reaction pathway involving the formation of rhodium carbene, the addition of HN3, and C=N bond formation.
Article
Chemistry, Multidisciplinary
Ming Hu, Boon Beng Tan, Shaozhong Ge
Summary: Selective defluoroborylation and asymmetric hydro-boration reactions have been developed for fluoroalkyl-substituted terminal alkenes, resulting in the synthesis of chiral alkylboronates with fluoroalkyl-substituted stereogenic carbon centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jianbo Liu, Matthew F. L. Parker, Sinan Wang, Robert R. Flavell, F. Dean Toste, David M. Wilson
Summary: The synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature has been reported. This method desulfurizes isothiocyanates with AgF and then acylates the formed derivative to afford N-trifluoromethyl amides, including previously inaccessible structures. The strategy provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners and could find application in the modification of advanced intermediates.
Review
Chemistry, Organic
Clement Ghiazza, Thierry Billard
Summary: Reagent design plays a crucial role in modern organofluorine chemistry, with a focus on introducing fluoroalkylthio or seleno groups efficiently and selectively. Among them, versatile fluoroalkyl thiosulfonates and selenosulfonates have been at the forefront of recent developments, showing rich chemical reactivity and wide applicability in various studies.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Fatima Lucio-Martinez, Wojciech Chaladaj
Summary: Fluorinated alkyl iodides have expanded beyond simple perfluoroalkyl iodides and new strategies for the activation of fluoroalkyl iodides towards radical formation have been introduced. These advances have greatly enriched the field of fluoroalkylation reactions and have led to the development of novel transformations of unsaturated systems.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
M. C. Bellucci, M. Frigerio, C. Castellano, F. Meneghetti, A. Sacchetti, A. Volonterio
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Nina Bono, Chiara Pennetta, Maria Cristina Belluci, Aurora Sganappa, Chiara Malloggi, Gabriella Tedeschi, Gabriele Candiani, Alessandro Volonterio
Article
Biochemical Research Methods
Zoia Shedania, Rusudan Kakava, Alessandro Volonterio, Tivadar Farkas, Bezhan Chankvetadze
JOURNAL OF CHROMATOGRAPHY A
(2020)
Article
Chemistry, Applied
Maria Cristina Bellucci, Alessandro Sacchetti, Alessandro Volonterio
ACS COMBINATORIAL SCIENCE
(2019)
Article
Biochemical Research Methods
Salome Pantsulaia, Khatia Targamadze, Nana Khundadze, Qetevan Kharaishvili, Alessandro Volonterio, Michael Chitty, Tivadar Farkas, Bezhan Chankvetadze
JOURNAL OF CHROMATOGRAPHY A
(2020)
Review
Infectious Diseases
Maria Cristina Bellucci, Alessandro Volonterio
Article
Chemistry, Multidisciplinary
Christopher M. Fellows, Karl-Heinz Hellwich, Stefano Meille, Graeme Moad, Tamaki Nakano, Michel Vert
PURE AND APPLIED CHEMISTRY
(2020)
Article
Biochemical Research Methods
Chiara Pennetta, Nina Bono, Federica Ponti, Maria Cristina Bellucci, Fiorenza Viani, Gabriele Candiani, Alessandro Volonterio
Summary: This study describes the design and synthesis of a novel class of aminoglycoside (AG)-based multifunctional vectors with high transfection efficiency and noticeable antibacterial properties. The results demonstrate excellent DNA condensation ability, good transfection performance with negligible cytotoxicity, as well as strong potential as antimicrobial agents.
BIOCONJUGATE CHEMISTRY
(2021)
Article
Chemistry, Organic
Eliana Lo Presti, Alessandro Volonterio, Monica Sani
Summary: This work reports the first synthesis of the complex amino acid labionin in a fully orthogonally protected and stereopure form. The structure incorporates five orthogonal protecting groups and three stereogenic centers, assembled using thia-Michael addition and electrophilic azidation. The successful synthesis is expected to enable the solid phase synthesis of both natural and synthetic analogues of labyrinthopeptins.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Mose Casalegno, Antonino Famulari, Stefano Valdo Meille
Summary: This study explores the polymorphism of P3HT through molecular dynamics modeling and suggests that MD may adequately describe the key features and relative stability of different crystal phases. Plausible interconversion mechanisms for rapid solid-solid or melting transitions are proposed, providing new insights into the fundamental research of polymer semiconductors.
Article
Chemistry, Organic
Alessio M. Caramiello, Maria Cristina Bellucci, Gaetano Cristina, Carlo Castellano, Fiorella Meneghetti, Matteo Mori, Francesco Secundo, Fiorenza Viani, Alessandro Sacchetti, Alessandro Volonterio
Summary: This study presents the synthesis of a collection of enantiomerically pure, systematically substituted hydantoins as structural privileged universal mimetic scaffolds. The synthesis relies on a selective condensation/cyclization process between isocyanates and aspartic acid diesters, followed by hydrolysis/coupling reactions with amines. Conformational studies showed that the hydantoin-based peptidomimetics are capable of projecting their substituents in positions superimposable to common protein secondary structures.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemical Research Methods
Carola Romani, Paola Gagni, Mattia Sponchioni, Alessandro Volonterio
Summary: In this study, we successfully functionalized PAMAM G2 and PAMAM G4 with fluorinated arginine-based building blocks, resulting in a novel PAMAM-based gene delivery vector. The conjugates showed improved binding capacity to plasmid DNA, reduced cytotoxicity, and enhanced gene transfection efficiency compared to undecorated PAMAM dendrimers. These findings are of great importance for gene delivery research and also have the potential for future application in F-19 magnetic resonance imaging.
BIOCONJUGATE CHEMISTRY
(2023)
Article
Chemistry, Organic
Alessio M. Caramiello, Maria Cristina Bellucci, Emerenziana Ottaviano, Silvia Ancona, Elisa Borghi, Alessandro Volonterio
Summary: Three model hydantoin-based universal peptidomimetics were designed, synthesized, and investigated for their conformation and antibacterial activity. The results demonstrated that these compounds could be promising antibiotics to combat drug resistance.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Alessio M. Caramiello, Maria Cristina Bellucci, Emerenziana Ottaviano, Silvia Ancona, Elisa Borghi, Alessandro Volonterio
Summary: In this study, three model hydantoin-based universal peptidomimetics were designed, synthesized, and investigated for their antibacterial activities against Gram-positive and Gram-negative bacteria strains. The results demonstrated that these compounds could potentially serve as promising antibiotics to combat emerging drug resistance.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Kaivin Hadidi, Maria Cristina Bellucci, Sergio Dall'Angelo, Alasdair Leeson-Payne, Justin J. Rochford, Jeffery D. Esko, Yitzhak Tor, Alessandro Volonterio
Summary: Guanidinoglycosides are non-cytotoxic molecular transporters capable of delivering high molecular weight bioactive cargos into cells at low nanomolar concentrations. The use of a stable guanidinoneomycin derivative armed with a highly specific maleimide moiety allows for efficient bioconjugation through thiol-maleimide click chemistry, expanding the field of application for these delivery vehicles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Xianda Wu, Minghong Chen, Shuiyun Zheng, Fu-Sheng He, Jie Wu
Summary: Here, we report a new method for synthesizing sulfilimines through an iron-catalyzed reaction between sulfenamides and 2,2,2-trifluor-diazoethane. This protocol features operational simplicity, mild conditions, and can be conducted in open air, providing a facile approach to trifloromethylated sulfilimines in moderate to good yields.
JOURNAL OF FLUORINE CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Ita Hajdin, Romana Pajkert, Haibo Mei, Jianlin Han, Gerd-Volker Roeschenthaler
Summary: A catalyst- and solvent-free 1,3-dipolar cycloaddition reaction using a bench-stable diazo reagent has been developed to obtain a series of novel 3H-pyrazoles bearing difluoromethyl phosphonate unit in moderate-to-excellent yields. This method provides an efficient and easy route to synthesize valuable compounds.
JOURNAL OF FLUORINE CHEMISTRY
(2024)
