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
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
Fabio Cuzzucoli, Leanne Racicot, John F. Valliant, Graham K. Murphy
Summary: A new class of fluorinated, cyclic N-methoxyimidates was synthesized through intramolecular fluorocyclization. The reaction achieved efficient cyclization at room temperature using unsaturated amides, a mono-fluoroiodane, and HFIP as the activator, resulting in products with up to 81% yield in a single step. Two product isomers were selectively obtained depending on the presence of an α-arene substituent.
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, 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
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)
Article
Chemistry, Applied
Chenyang Wang, Han Wang, Carsten Bolm
Summary: This study efficiently prepares sulfoximines with nitrogen-bound alpha-ketoester units in air using a one-pot reaction sequence, with the key step being the in-situ formation of hypervalent iodine reagents serving as electrophilic sulfoximidoyl sources.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Bing Zu, Jie Ke, Yonghong Guo, Chuan He
Summary: Anodic oxidation enables the synthesis and derivatization of hypervalent iodine(III) reagents from aryl iodides under mild electrochemical conditions. This method offers a straightforward and sustainable approach by using only electrons as the oxidation reagents, thus avoiding the use of expensive or hazardous chemical oxidants.
CHINESE JOURNAL OF CHEMISTRY
(2021)
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
Xia Wang, Peng Yang, Bo Hu, Qian Zhang, Dong Li
Summary: A novel transformation of primary amides to secondary amides was developed using hypervalent iodine reagents, promoting a Hofmann-type rearrangement to generate an isocyanate intermediate which was then trapped by a carboxylic acid from the same reagent to provide the corresponding secondary amides. This method not only offers an easy and efficient route for synthesizing secondary amides from primary amides, but also reveals novel reactivities of hypervalent iodine reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Chenyang Wang, Peng Shi, Carsten Bolm
Summary: In this study, dichloro- and dibromomethane were utilized as halogen sources to convert NH-sulfoximines to N-halo derivatives, using an in situ formed sulfoximidoyl-containing hypervalent iodine reagent under visible light. The reactions were carried out in air without the need for catalysts or additives, and the products were obtained in good to excellent yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Applied
Akira Yoshimura, Akio Saito, Viktor V. Zhdankin
Summary: Hypervalent iodine compounds, particularly those based on the benziodoxole heterocyclic system, are widely used as reagents and catalysts in modern organic chemistry. These cyclic hypervalent iodine reagents exhibit higher stability compared to their acyclic analogues, allowing for the safe handling and preparation of reagents with special ligands such as azido, cyano, and trifluoromethyl groups. They have been utilized for the transfer of substituents on hypervalent iodine to organic substrates under various reaction conditions. This review focuses on the recent synthetic applications of cyclic hypervalent iodine(III) reagents with different ligands, including N-3, NHR, CN, CF3, SCF3, OR, OAc, ONO2, and C(=N-2)CO2R, mainly in the past 5 years.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zhouhao Wang, Junping Hu, Jing Liu, Yew Von Lim, Haobin Song, Ye Wang, Tingting He, Chunlai Huang, Xinwen Yan, Daohong Zhang, Shaozhuan Huang
Summary: In this study, a hypervalent iodine compound named iodosobenzene (PhIO) was proposed to enhance the performance of Li-S batteries by regulating the electrochemistry of LiPSs. PhIO exhibited practical advantages such as low cost, commercial availability, environmental friendliness, and chemical stability. The results showed that the lone pair electrons of oxygen atoms in PhIO played a critical role in forming a strong Lewis acid-base interaction with terminal Li in LiPSs. Additionally, PhIO could be easily converted to nanoparticles and loaded on a carbon nanotube scaffold, resulting in an interlayer that obstructed LiPSs penetration, enhanced electrolyte wettability and Li+ conduction. The Li-S battery based on the PhIO@CNT interlayer exhibited stable cycling and excellent rate performance.
Review
Chemistry, Multidisciplinary
Cai Zhang, Jie-Ping Wan
Summary: Diazomethyl-substituted iodine(III) compounds with electron-withdrawing groups have potential reaction abilities and can be used as key intermediates in organic synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Katja Reinhardt, Sebastian Koller, Philippe Klein, Corvin Lossin, Julia Gatzka, Philipp J. Altmann, Alexander Poethig, Lukas Hintermann
Summary: The study focuses on the attachment of di(1R)-menthylphosphino fragments to molecular scaffolds to create homochiral, bulky phosphine ligands for potential applications in coordination chemistry and transition-metal catalysis. Various transformations and reactions involving dimenthylphosphine P-oxide are explored, leading to the synthesis of new ligands and complexes with specific reactivity profiles due to the presence of menthyl groups. This approach shows promise for use in model palladium-catalyzed coupling reactions, with ligand 22 exhibiting high enantioselectivity in a specific biaryl-forming reaction.
Article
Chemistry, Multidisciplinary
Anish Das, Chris Weise, Matthias Polack, Raphael D. Urban, Benjamin Krafft, Sadat Hasan, Hannes Westphal, Rico Warias, Simon Schmidt, Tanja Gulder, Detlev Belder
Summary: This study presents an approach for the online coupling of digital microfluidics with mass spectrometry. The technique uses a chip-integrated microspray hole to analyze a portion of a sample droplet by mass spectrometry. The method eliminates the need for chip disassembly or capillary emitters, allowing the advantages of digital microfluidics to be retained during mass spectrometry analysis. The developed coupling technique has been successfully applied to various applications, including organic synthesis and protein analysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Biochemistry & Molecular Biology
Paul M. D'Agostino, Catharina J. Seel, Xiaoqi Ji, Tanja Gulder, Tobias A. M. Gulder
Summary: This study elucidates the biosynthetic process of furanolide assembly, providing insights into the function and mechanism of key enzymes. It expands the biocatalytic toolbox for gamma-butyrolactone formation and lays the foundation for targeted discovery and enzymatic synthesis of furanolides.
NATURE CHEMICAL BIOLOGY
(2022)
Article
Chemistry, Physical
Sebastian J. Weishaeupl, Yang Cui, Simon N. Deger, Hamad Syed, Aleksandr Ovsianikov, Juergen Hauer, Alexander Poethig, Roland A. Fischer
Summary: Multiphoton absorption (MPA) is of great interest in modern materials research, and metal-organic frameworks and coordination polymers (CPs) are potential materials to overcome the limitations of commonly used chromophore molecules. This article reports the synthesis and characterization of three new highly MPA-active CPs, and demonstrates their large two-photon absorption cross-sections, which are among the highest reported for CPs to date.
CHEMISTRY OF MATERIALS
(2022)
Article
Biochemistry & Molecular Biology
Jelena Lazic, Sanja Skaro Bogojevic, Sandra Vojnovic, Ivana Aleksic, Dusan Milivojevic, Martin Kretzschmar, Tanja Gulder, Milos Petkovic, Jasmina Nikodinovic-Runic
Summary: Prodigiosins are bacterial secondary metabolites with remarkable biological activities and color. In this study, prodigiosin (PG) was successfully produced, purified, and characterized from Serratia marcescens ATCC 27117 strain. Novel brominated derivatives of PG were also synthesized. PG and its brominated derivatives showed potential in cancer treatment but had low selectivity against healthy cells. The brominated derivatives exhibited improved toxicity compared to PG, which is a significant finding for further optimization of bacterial prodigiosins.
Article
Chemistry, Organic
Martin Kretzschmar, Tanja Gulder
Summary: In this article, we present a generally applicable umpolung method for the alpha-functionalization of ketones, using cyclic hypervalent fluoro-iodane as the key reagent. The reaction not only enables various alkene functionalizations, but also leads to the formation of alpha-functionalized ketones as minor side products. Further investigation revealed a directed umpolung of pyridyl ketones by the fluoro-iodane, which was facilitated by unexpected non-covalent interactions between the nucleophile, substrate, and iodane.
Review
Biochemistry & Molecular Biology
Joerg Matysik, Luca Gerhards, Tobias Theiss, Lisa Timmermann, Patrick Kurle-Tucholski, Guzel Musabirova, Ruonan Qin, Frank Ortmann, Ilia A. Solov'yov, Tanja Gulder
Summary: This review summarizes the phenomenon of nuclear hyperpolarization occurring in chemical reactions, known as CIDNP or photo-CIDNP if driven by light. It occurs in both liquid and solid-state, often involving electron transfer systems with flavins as electron acceptors. The article explains the properties of flavins, their occurrence in spin-correlated radical pairs (SCRPs), and the potential involvement of flavin-carrying SCRPs in animal magneto-reception at Earth's magnetic field.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Multidisciplinary Sciences
Andreas M. M. Arnold, Philipp Dullinger, Aniruddha Biswas, Christian Jandl, Dominik Horinek, Tanja Gulder
Summary: The authors report the synthesis of (poly)cyclic carbon frameworks using in-situ formed fluorinated-alcohol-amine supramolecular clusters that mimic terpene cyclases. Terpene cyclases are highly efficient and selective catalysts in natural product synthesis. The supramolecular clusters act as artificial cyclases, triggering enzyme-like reactivity and selectivity by controlling substrate conformation in solution.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Medicinal
Valeria Scalcon, Riccardo Bonsignore, Jana Aupic, Sophie R. Thomas, Alessandra Folda, Alexandra A. Heidecker, Alexander Pothig, Alessandra Magistrato, Angela Casini, Maria Pia Rigobello
Summary: Two new hybrid metallodrugs of Au(III)(AuTAML)and Cu(II) (CuTAML) were designed to synergize the anticancer activity of both the metal centerand the organic ligand. These drugs showed antiproliferative effects against breast cancer cells and retained binding activity to estrogen receptor (ERα). Furthermore, they exhibited different reactivities and cytotoxic potencies, but displayed a capacity to induce mitochondrial damage.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
News Item
Chemistry, Multidisciplinary
Rachel C. Epplin, Tanja Gulder
Summary: Fluorination strategies are crucial for pharmaceutical synthesis. Iodine catalysis has been widely used for introducing gem-difluoro groups, but it is limited to styrenes. The hypervalent iodane-catalysed difluorination of enynes now provides access to diverse homopropargylic difluorides.
Article
Chemistry, Physical
Denise Lovison, Tobias Berghausen, Sophie R. Thomas, Jonathan Robson, Markus Drees, Christian Jandl, Alexander Poethig, Patrick Mollik, Dominik P. Halter, Walter Baratta, Angela Casini
Summary: In this study, water-soluble organometallic Ru(II) complexes were synthesized and found to act as anticancer agents by catalyzing transfer hydrogenation reactions with biomolecules. The structure-activity relationship and reaction mechanism were investigated, and the compounds were also tested for their anticancer activity in vitro.
Article
Multidisciplinary Sciences
Shangpu Liu, Mikael Kepenekian, Stanislav Bodnar, Sascha Feldmann, Markus W. Heindl, Natalie Fehn, Jonathan Zerhoch, Andrii Shcherbakov, Alexander Poethig, Yang Li, Ulrich W. Paetzold, Aras Kartouzian, Ian D. Sharp, Claudine Katan, Jacky Even, Felix Deschler
Summary: This study reveals the unique photoluminescence properties of hybrid perovskite semiconductor materials, which can achieve high luminescence yields and circularly polarized photoluminescence at room temperature. The excellent photoluminescence performance is attributed to the suppression of nonradiative loss channels and the high rates of radiative recombination. These findings pave the way for high-performance solution-processed photonic systems and chiral-spintronic logic at room temperature.
Article
Chemistry, Multidisciplinary
Julia Binder, Aniruddha Biswas, Tanja Gulder
Summary: In this study, a novel chlorination-induced polyene cyclization method is proposed, utilizing HFIP-chloroiodane networks to mimic terpene cyclases. Various different alkenes were converted with high selectivities (up to d.r. > 95:5). The cyclization platform was also successfully extended to structurally challenging terpenes and terpenoid carbon frameworks.
Review
Materials Science, Multidisciplinary
Sebastian J. Weishaeupl, David C. Mayer, Yang Cui, Pushpendra Kumar, Harald Oberhofer, Roland A. Fischer, Jurgen Hauer, Alexander Poethig
Summary: This review presents recent advances in metal-organic frameworks (MOFs) and coordination polymers (CPs) regarding their response properties to multiphoton absorption (MPA). It covers the theoretical background of MPA absorbing linker molecules, the effect of excitonic coupling within a rigid framework assembly, and compares different scanning and non-scanning measurement techniques for two-photon absorption (TPA) spectroscopy. Additionally, it comprehensively presents the latest progress of linker-based MPA materials and their relationship with framework structure and MPA cross section.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Inorganic & Nuclear
Brech Aikman, Riccardo Bonsignore, Ben Woods, Daniel Doellerer, Riccardo Scotti, Claudia Schmidt, Alexandra A. Heidecker, Alexander Poethig, Edward J. Sayers, Arwyn T. Jones, Angela Casini
Summary: Research focused on designing new metallosupramolecular structures for drug delivery. Two self-assembled metal cages capable of encapsulating anticancer drugs have been synthesized and characterized. The stability and intracellular localization of these structures have been confirmed, and their antiproliferative activity has been investigated.
DALTON TRANSACTIONS
(2022)