Correction
Chemistry, Multidisciplinary
Nina Declas, John R. J. Maynard, Laure Menin, Natalia Gasilova, Sebastian Gotze, Jakob L. Sprague, Pierre Stallforth, Stefan Matile, Jerome Waser
Summary: Correction for the paper 'Tyrosine bioconjugation with hypervalent iodine' by Nina Declas et al. presents an improved method for the effective conjugation of tyrosine with hypervalent iodine by rectifying the errors in the original study.
Article
Chemistry, Organic
Thibaut Duhail, Jorna Kalim, Jerome Marrot, Bruce Pegot, Emmanuel Magnier, Elsa Anselmi
Summary: This study describes hypervalent iodine compounds with specific ligands, investigating the influence of these groups on the stability of cyclic structure and highlighting the crucial role of the trifluoromethyl chain as an efficient ligand. The structure and reactivity of the new skeletons are discussed in detail.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ilias Koutsopetras, Abhaya Kumar Mishra, Rania Benazza, Oscar Hernandez-Alba, Sarah Cianferani, Guilhem Chaubet, Stefano Nicolai, Jerome Waser
Summary: Peptide and protein bioconjugation is increasingly important in the pharmaceutical industry. This study introduces the crosslinking ethynylbenziodazolone (EBZ) reagent JW-AM-005 for selective conjugation of peptides and proteins using cysteine residues. The reagent allows for the formation of peptide dimers or stapled peptides under mild and tuneable conditions. Additionally, it demonstrates high regioselectivity in the rebridging of antibody fragments, surpassing commonly used reagents for this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Emmanuelle M. D. Allouche, Elija Grinhagena, Jerome Waser
Summary: Hypervalent iodine compounds are powerful reagents for biomolecule functionalization, with recent advances in peptide and protein modification up to June 2021. Their use as group transfer or oxidizing reagents targeting polar, aromatic, or aliphatic amino acids and peptide termini is discussed in this Minireview.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Irina A. Mironova, Stefan F. Kirsch, Viktor V. Zhdankin, Akira Yoshimura, Mekhman S. Yusubov
Summary: This review summarizes recent approaches to the direct synthesis of organic azides using hypervalent iodine reagents. The first part discusses the use of unstable azidoiodinanes generated in situ, while the second part focuses on the application of stable azidobenziodoxoles as azidating reagents. The use of azidobenziodoxoles allows for selective direct azidation of specific bonds under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Javier Ceballos, Elija Grinhagena, Gontran Sangouard, Christian Heinis, Jerome Waser
Summary: The study introduces a novel method for preparing stapled peptides using bis-functional hypervalent iodine reagents for two-component cysteine-cysteine and cysteine-lysine stapling. This method does not require pre-functionalization or metal catalysis, and the products are stable for purification and isolation, with post-stapling modifications possible through various methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Chenyang Wang, Yongliang Tu, Ding Ma, Chaimae Ait Tarint, Carsten Bolm
Summary: The reaction between [Bis(difluoroacetoxy)iodo]benzene and NH-sulfoximines produces hypervalent iodine(III) reagents, which can transfer difluoroacetoxy and sulfoximidoyl groups to styrenes with high regioselectivity under photocatalysis. Mechanistic investigations suggest the involvement of radicals and highlight the importance of the difluoroacetoxy group in the iodine reagent.
Article
Chemistry, Multidisciplinary
Oleg O. Shyshkov, Alexander A. Kolomeitsev, Berthold Hoge, Enno Lork, Axel Haupt, Mira Kessler, Gerd-Volker Roeschenthaler
Summary: Phosphoranides are hypervalent species that can serve as model compounds for intermediates or transition states in nucleophilic substitution reactions. This study reports the syntheses and properties of stable trifluoromethylphosphoranide salts, and investigates their reactivity towards electrophiles. The structures and dynamics of these compounds are determined using X-ray crystallography and NMR spectroscopy.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jessica Neufeld, Constantin. G. G. Daniliuc, Ryan Gilmour
Summary: This study presents a regioselective fluorocyclisation of beta,gamma-unsaturated oximes through I(I)/I(III) catalysis, using p-iodotoluene as a cost-effective catalyst, Selectfluor((R)) as the oxidant, and an amine.HF complex as the fluoride and Bronsted acid source. The transformation produces 5-fluoromethylated isoxazolines, with a range of aliphatic and aromatic systems yielding up to 56%.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Lipiao Bao, Baolin Zhao, Bowen Yang, Marcus Halik, Frank Hauke, Andreas Hirsch
Summary: A series of hypervalent iodine compounds have been reported as highly efficient for diversified graphene patterning, generating reactive radicals for controlled chlorination, hydroxylation, and trifluoromethylation. The highly functionalized graphene nanoarchitectures allow for reversible attachment of functional entities with full control over stored chemical information. This work provides an exciting approach for target 2D functionalization and modulation of graphene using suitable hypervalent iodine compounds.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Kumar Bhaskar Pal, Ester Maria Di Tommaso, A. Ken Inge, Berit Olofsson
Summary: We report an efficient radical-mediated C-C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C-C bond formation is stereospecific and proceeds through a concerted radical coupling transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yanyao Cai, Wenjie Zhu, Shujuan Zhao, Chanjuan Dong, Zhenchuang Xu, Yanchuan Zhao
Summary: A difluorocarbene-mediated cascade cyclization reaction has been developed for rapid synthesis of gem-difluorinated 3-coumaranone derivatives, showing its potential application in the late-stage modification of diethylstilbestrol. Mechanistic studies revealed the multiple crucial roles played by the Ruppert-Prakash reagent.
Article
Chemistry, Multidisciplinary
Lachlan Sharp-Bucknall, Tania, Jason L. Dutton
Summary: This article describes the synthesis and structural characterization of NO2-PhI(OTf)(2), a compound that is resistant to decomposition and has higher reactivity than previously misidentified PhI(OTf)(OAc), confirming the non-existence of PhI(OTf)(2) as an intermediate in oxidation reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nagarajan Ramkumar, Ketrina Plantus, Melita Ozola, Anatoly Mishnev, Vizma Nikolajeva, Maris Senkovs, Maksim Oseka, Janis Veliks
Summary: A photo-redox catalyzed radical C-H monofluoromethylation of heterocycles is reported, demonstrating the importance of the monofluoromethyl unit in medicinal and drug discovery purposes. The synthesized compounds show promising antimicrobial and anticancer activities.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nagarajan Ramkumar, Ketrina Plantus, Melita Ozola, Anatoly Mishnev, Vizma Nikolajeva, Maris Senkovs, Maksim Oseka, Janis Veliks
Summary: We report a visible-light photoredox catalytic method for the mild and direct modification of medicinally relevant heterocycles by transferring monofluoromethyl radicals using an iodine(iii) reagent containing monofluoroacetoxy ligands. This approach enriches the synthesis of structurally diverse heteroaromatics incorporating monofluoromethyl groups and demonstrates the potential of direct C-H radical monofluoromethylation for late-stage modifications of medicinally relevant biomolecules and drugs.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Kheironnesae Rahimidashaghoul, Iveta Klimankova, Martin Hubalek, Vaclav Matousek, Josef Filgas, Petr Slavicek, Tomas Slanina, Petr Beier
Summary: The study utilized different reagents for fluoroalkylation, with the photochemical process showing better selectivity. However, side reactions still occurred in the presence of cysteine residues.
Article
Chemistry, Multidisciplinary
Jorna Kalim, Thibaut Duhail, Ewa Pietrasiak, Elsa Anselmi, Emmanuel Magnier, Antonio Togni
Summary: A study has discovered a method for direct trifluoromethylation of various aliphatic alcohols using a hypervalent iodosulfoximine reagent, resulting in the efficient synthesis of corresponding ethers.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Yannick Kraemer, Emily Nicole Bergman, Antonio Togni, Cody Ross Pitts
Summary: In the development of synthetic methods, researchers discovered a mild and inexpensive oxidative fluorination method based on potassium fluoride and trichloroisocyanuric acid (TCICA), which enabled the synthesis of pentafluorosulfanyl (SF5) compounds. Further exploration led to the discovery of its application in the synthesis of other fluorinated heteroatoms. Ultimately, it was found that this method can be used to synthesize SF5Cl.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Martin Posta, Vaclav Zima, Lenka Postova Slavetinska, Marika Matousova, Petr Beier
Summary: The synthesis of a sulfur-containing karrikin compound and a class of karrikin derivatives with sulfur heteroatoms incorporated into the core backbone is reported. Their biological activity in inhibiting acetylcholinesterase is evaluated.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Vladimir Motornov, Petr Beier
Summary: NH-1,2,3-Triazoles undergo ring cleavage in reactions with fluorinated acid anhydrides and can be used for the synthesis of fluoroalkylated compounds.
Article
Chemistry, Organic
Lukas Janecky, Athanasios Markos, Blanka Klepetar, Petr Beier
Summary: 4-Aryl-5-allyl-N-fluoroalkyl-1,2,3-triazoles were synthesized through a three-component reaction of fluoroalkyl azides, copper acetylides, and allyl halides. These compounds underwent aluminum halide-mediated transformation to N-(4-halo-2-aryl-cyclopentenyl) imidoyl halides by cyclization of vinyl cation intermediates, followed by halide capture. The cyclic products could be further utilized for the synthesis of N-alkenyl amides, amidines, isoquinolines, and tetrazoles, or for the subsequent modification of the cyclopentene ring.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Vladimir Motornov, Petr Beier
Summary: Metal-free cascade reaction of NH-1,2,3-triazoles with one-carbon electrophiles, such as thiophosgene and triphosgene, generates N-vinylated ring cleavage products. N-vinylisothiocyanates can be synthesized from NH-triazoles and thiophosgene using this approach. A variety of multifunctional compounds, such as N-vinylcarbamates, unsymmetrical vinylureas, carbamothioates, etc. were prepared by a one-pot method from NH-triazoles, triphosgene, and nucleophiles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Mykyta Ziabko, Blanka Klepetarova, Petr Beier
Summary: A new stable fluorinated azide called azidodifluoromethylphenyl sulfone was synthesized from difluoromethyl phenyl sulfone on a multi-gram scale. This azide showed synthetic utility in the preparation of N-difluoro-(phenylsulfonyl)-methyl-1,2,3-triazoles through azide-alkyne cycloaddition reactions. It also served as a synthetic equivalent of the azidodifluoromethylanion.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Vladimir Motornov, Blanka Klepetarova, Petr Beier
Summary: High-valent Cu(III) trifluoromethyl complexes with 1,3-diketonates as bidentate oxygen donor ligands LCu(III)(CF3)(2) were synthesized and characterized. They exhibit bench stability and solubility in organic solvents. The reactivity of Cu(III) trifluoromethyl diketonates in radical and radical-polar crossover trifluoromethylation reactions was demonstrated, along with the direct C-H trifluoromethylation of electron-rich arenes and indoles and the azolo- and oxy-trifluoromethylation of terminal alkynes and aromatic thiol using LCu(III)(CF3)(2) under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Elena Shaitanova, Vaclav Matousek, Tadeas Herentin, Martin Adamec, Robert Matyas, Blanka Klepetarova, Petr Beier
Summary: This article introduces a new method for preparing fluorinated azidoethane and its application in various reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Vladimir Motornov, Radek Pohl, Blanka Klepetarova, Petr Beier
Summary: Elusive N-acyl-1,2,3-triazoles formed by direct acylation of NH-1,2,3-triazoles were isolated and characterized. Thermodynamic N2 isomers were found to be preferred. Direct evidence of interconversion between N1- and N2-acyltriazoles confirmed their usefulness in denitrogenative transformations. An efficient synthesis of enamido triflates from NH-triazoles via N2-acyl-1,2,3-triazole intermediates was developed.
CHEMICAL COMMUNICATIONS
(2023)
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)
Review
Chemistry, Multidisciplinary
Vladimir Motornov, Petr Beier
Summary: This review focuses on the utilization of NH-1,2,3-triazoles as easily accessible building blocks for denitrogenative ring cleavage transformations, providing multifunctionalized nitrogen heterocycles and N-alkenyl compounds. These processes offer a convenient route to a range of pharmaceutically relevant heterocyclic cores and N-alkenyl compounds by leveraging the ready availability of NH-1,2,3-triazoles. The synthetic usefulness of in situ acylated NH-1,2,3-triazoles as viable alternatives to widely explored N-sulfonyl-1,2,3-triazoles in ring cleavage processes is highlighted.
Article
Chemistry, Multidisciplinary
Vladimir Motornov, Petr Beier
Summary: An efficient one-pot method has been developed for the synthesis of 2-fluoroalkyloxazoles. This method offers a mild and high-yielding approach to prepare structurally diverse fluoroalkylated oxazoles from readily available starting reagents. Furthermore, an alternative direct method using acetonitrile as the solvent has been described for the synthesis of fluoroalkylated oxazoles from electron-rich NH-triazoles.
NEW JOURNAL OF CHEMISTRY
(2022)
