Article
Chemistry, Multidisciplinary
Shobhan Mondal, Ester Maria Di Tommaso, Berit Olofsson
Summary: Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S-diarylation, enabling the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl(vinyl) sulfides. A one-pot strategy combining transition-metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Melissa Chasse, Anna Pees, Anton Lindberg, Steven H. H. Liang, Neil Vasdev
Summary: Positron emission tomography (PET) is a powerful imaging tool used for drug discovery, clinical diagnosis, and disease monitoring. However, the lack of compatible methods and precursors for radiolabeling with fluorine-18 has limited the development of radiotracers. The radiolabeling of electron-rich (hetero)aromatic rings has been a long-standing challenge in producing PET radiopharmaceuticals. In this personal account, the history and applications of spirocyclic iodonium ylide precursors are discussed for the incorporation of fluorine-18 into complex non-activated (hetero)aromatic rings.
Article
Chemistry, Organic
Thomas J. Kuczmera, Andreas Boelke, Boris J. Nachtsheim
Summary: This study presents a systematic investigation of ethynyl N-heterocycle-substituted-lambda(3)-iodanes (ENHIs) and evaluates their potential applications in alkyne group transfer reactions through synthesis and reactivity assessment.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yulia A. Vlasenko, Thomas J. Kuczmera, Nikita S. Antonkin, Rashid R. Valiev, Pavel S. Postnikov, Boris J. Nachtsheim
Summary: Here, the application of azole-stabilized diaryliodonium salts with additional thiophene-2-yl-ligands as metal-free nucleophilic arylation substrates is presented. In addition to their synthesis, their use in chemoselective nitrations, oxygenations, aminations, and thiolations under umpolung conditions is demonstrated. Convenient one-pot procedures based on their in situ formation are also discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Thomas J. Kuczmera, Annalena Dietz, Andreas Boelke, Boris J. Nachtsheim
Summary: This study presents a systematic investigation of imidazo-and pyrazoloiodazinium salts. The researchers successfully synthesized these novel cyclic iodonium salts in mono-and dicationic forms and gained in-depth structural information through single-crystal analysis. They also demonstrated the ring opening of the heterocycle-bridged iodonium species. Furthermore, they showed highly delicate post-oxidation functionalizations retaining the hypervalent iodine center for a specific set of dicationic imidazoiodaziniums.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andreas Boelke, Thomas J. Kuczmera, Enno Lork, Boris J. Nachtsheim
Summary: The article explores the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts, particularly as potent XB-donors in halogen-bond catalysis. Among the variety of NHISs tested, N-methylated dicationic NHISs exhibited the highest reactivity in all investigated catalytic applications, surpassing previously described monodentate XB-donors based on iodine(I) and (III) as well as the strong Lewis acid BF3.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
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, 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
Shubhendu S. Karandikar, Avik Bhattacharjee, Bryan E. Metze, Nicole Javaly, Edward J. Valente, Theresa M. McCormick, David R. Stuart
Summary: Diarylhalonium compounds play important roles as reagents and catalysts in organic synthesis, with the key reactivity of the three center, four electron bond requiring refinement for broader applicability. The combination of Density Functional Theory, Natural Bond Orbital Theory, and X-ray structure data can provide insights into the bonding and structure of these compounds.
Article
Chemistry, Inorganic & Nuclear
Guobi Li, Arnold L. Rheingold, John D. Protasiewicz
Summary: This report examines the impact of introducing nitro groups on the solid state aggregation of two common types of cyclic hypervalent iodine compounds. The study found that while the nitro groups increased the electrophilicity of the iodine center, interactions with counterions or solvent molecules were more preferred.
Article
Chemistry, Applied
Dmitry I. Bugaenko, Alexander V. Karchava
Summary: This study presents a simple and efficient method for the preparation of highly substituted tertiary arylphosphines. The method involves the arylation of tertiary aryl and alkyl phosphines with aryl(mesityl)iodonium triflates under blue light irradiation, followed by a retro-Michael reaction initiated by DBU. The method is mild, transition-metal-free, and shows high selectivity, broad functional group compatibility, as well as scalability and applicability to substrates with different electronic and steric nature.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Thomas Delouche, Elsa Caytan, Marie Cordier, Thierry Roisnel, Gregory Taupier, Yann Molard, Nicolas Vanthuyne, Boris Le Guennic, Muriel Hissler, Denis Jacquemin, Pierre-Antoine Bouit
Summary: We report a straightforward synthesis method for novel P-heterocycles. These compounds exhibit good stability and can be post-functionalized with different substituents. They are also suitable for the preparation of more complex polyaromatic scaffolds. Our study shows that molecular engineering can not only tune the optical properties of these compounds but also impart them with special optical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Mohamed Elsherbini, Wesley J. Moran
Summary: Cyclic and acyclic diaryliodonium salts were synthesized efficiently without the need for chemical oxidants or generation of chemical waste, with yields ranging from very good to excellent. When scaled-up to 10 mmol, over four grams of product with purity above 95% were obtained in less than three hours, and the solvent mixture could be recycled multiple times with minimal reduction in yield.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Medicinal
Malvika Sardana, Louise Breuil, Sebastien Goutal, Maud Goislard, Mikhail Kondrashov, Etienne Marchal, Florent L. Besson, Christophe Dugave, Gail Wrigley, Anna C. Jonson, Bertrand Kuhnast, Magnus Schou, Nicolas Tournier, Charles S. Elmore, Fabien Caille
Summary: A spirocyclic hypervalent iodine precursor was synthesized for the isotopic labeling of Crizotinib, and PET imaging demonstrated the feasibility of [F-18](R)-Crizotinib for in vivo imaging. The study suggests that this method can be used for further research on enhancing the brain penetration of Crizotinib.
Article
Chemistry, Multidisciplinary
Matic Lozinsek, Helene P. A. Mercier, Gary J. Schrobilgen
Summary: The coordination chemistry of KrF2 is limited compared to XeF2, but in this study, new mixed krypton/xenon compounds were synthesized where KrF2 acts as a ligand coordinating to xenon atoms. This extends the XeF2-KrF2 analogy and introduces a new class of coordination compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Young-Do Kwon, Jeongmin Son, Mijin Yun, Joong-Hyun Chun
TETRAHEDRON LETTERS
(2018)
Article
Chemistry, Organic
Young-Do Kwon, Jeongmin Son, Joong-Hyun Chun
Article
Chemistry, Organic
Young-Do Kwon, Jeongmin Son, Joong-Hyun Chun
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Radiology, Nuclear Medicine & Medical Imaging
Anton Lindberg, Shuiyu Lu, Sangram Nag, Magnus Schou, Jeih-San Liow, Sami S. Zoghbi, Michael P. Frankland, Robert L. Gladding, Cheryl L. Morse, Akihiro Takano, Nahid Amini, Charles S. Elmore, Yong Sol Lee, Robert B. Innis, Christer Halldin, Victor W. Pike
NUCLEAR MEDICINE AND BIOLOGY
(2019)
Article
Radiology, Nuclear Medicine & Medical Imaging
Dongwoo Kim, Joong-Hyun Chun, Se Hoon Kim, Ju Hyung Moon, Seok-Gu Kang, Jong Hee Chang, Mijin Yun
EUROPEAN JOURNAL OF NUCLEAR MEDICINE AND MOLECULAR IMAGING
(2019)
Article
Chemistry, Multidisciplinary
Jimmy E. Jakobsson, Shuiyu Lu, Sanjay Telu, Victor W. Pike
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Cell Biology
Shuiyu Lu, Mohammad B. Haskali, Kevin M. Ruley, Nicolas J-F Dreyfus, Susan L. DuBois, Soumen Paul, Jeih-San Liow, Cheryl L. Morse, Aneta Kowalski, Robert L. Gladding, Jeremy Gilmore, Adrian J. Mogg, S. Michelle Morin, Peter J. Lindsay-Scott, J. Craig Ruble, Nancy A. Kant, Sergey Shcherbinin, Vanessa N. Barth, Michael P. Johnson, Maria Cuadrado, Enrique Jambrina, Andrew J. Mannes, Hugh N. Nuthall, Sami S. Zoghbi, Cynthia D. Jesudason, Robert B. Innis, Victor W. Pike
SCIENCE TRANSLATIONAL MEDICINE
(2020)
Article
Chemistry, Organic
Young-Do Kwon, Min Ho Jeon, Nam Kyu Park, Jeong Kon Seo, Jeongmin Son, Young Hoon Ryu, Sung You Hong, Joong-Hyun Chun
Article
Chemistry, Organic
Min Ho Jeon, Young-Do Kwon, Min Pyeong Kim, Gianluca Bartolini Torres, Jeong Kon Seo, Jeongmin Son, Young Hoon Ryu, Sung You Hong, Joong-Hyun Chun
Summary: The study presents a successful synthesis of various sulfamoyl [F-18]fluorides using an F-18/F-19 isotopic exchange approach, improving synthetic efficiency with radiochemical yields up to 97%. This late-stage labeling protocol offers an efficient route to diversify the chemical library possessing sulfamoyl functionalities by incorporating nucleophilic F-18 within nitrogen-containing sulfur(VI) frameworks.
Article
Multidisciplinary Sciences
Jae Bin Lee, Gun Ha Kim, Ji Hwan Jeon, Seo Yeong Jeong, Soochan Lee, Jaehyun Park, Doyoung Lee, Youngkook Kwon, Jeong Kon Seo, Joong-Hyun Chun, Seok Ju Kang, Wonyoung Choe, Jan-Uwe Rohde, Sung You Hong
Summary: The authors present a transition-metal-free, radical relay pi-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts. This method offers a solution to the limitation of low reactivity in unactivated azines.
NATURE COMMUNICATIONS
(2022)
Article
Radiology, Nuclear Medicine & Medical Imaging
Dongwoo Kim, Joong Hyun Chun, Ju Hyeon Yi, Hae Young Ko, Jee-In Chung, Misu Lee, Yongmin Mason Park, Min-Ho Nam, Jisu Kim, Seon Yoo Kim, Youngjoo Park, Ju Hyung Moon, Seok-Gu Kang, Jong Hee Chang, C. Justin Lee, Se Hoon Kim, Mijin Yun
Summary: C-11-ACE PET/CT is an imaging biomarker that can characterize reactive astrogliosis in different types of gliomas. High C-11-ACE uptake is associated with high-grade IDH1-wt tumors, allowing differentiation from high-grade IDH1-mt and low-grade gliomas. Low C-11-ACE uptake in ODs is advantageous in overcoming the limitations of radiolabeled amino acid tracers.
CLINICAL NUCLEAR MEDICINE
(2022)
Article
Chemistry, Medicinal
Meijuan Jiang, Shuiyu Lu, Sanjay Telu, Victor W. Pike
Summary: Development of a PET radioligand for imaging PDE4D is important for drug discovery and understanding neuropsychiatric disorders. The existing radioligand, [11C]T1650, shows unstable quantification in humans, necessitating structural improvements. By formulating and optimizing an empirical equation, we successfully predicted and obtained 14 new compounds with high inhibitory potency. Eight of these compounds were deemed suitable for future radiolabeling and evaluation as PDE4D PET radioligands.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Medicine, Research & Experimental
Su Bin Kim, In Ho Song, Seon Yoo Kim, Hae Young Ko, Hee Seup Kil, Dae Yoon Chi, Frederik L. Giesel, Klaus Kopka, Alexander Hoepping, Joong-Hyun Chun, Hyun Soo Park, Mijin Yun, Sang Eun Kim
Summary: Several radiolabeled PSMA-targeted agents have been developed for detecting prostate cancer and targeted radionuclide therapy. This study characterized the pharmacokinetics and radiation dose of [18F]PSMA-1007 in prostate tumor-bearing mice. The kidney showed the highest accumulation of [18F]PSMA-1007, and the concentration in the tumor reached its peak at 112 min after injection. Treatment with a PSMA inhibitor significantly decreased [18F]PSMA-1007 uptake in the tumor.
MOLECULAR PHARMACEUTICS
(2022)
Article
Chemistry, Organic
Min Pyeong Kim, Hojin Cho, Swatilekha Kayal, Min Ho Jeon, Jeong Kon Seo, Jeongmin Son, Jinsil Jeong, Sung You Hong, Joong-Hyun Chun
Summary: We describe a direct radiofluorosulfurylation method that synthesizes 18F-labeled fluorosulfuryl derivatives from phenols and amines using an [18F]FSO2+ transfer agent generated in situ. Nucleophilic radiofluorination can be achieved even in a hydrous organic medium, eliminating the need for azeotropic drying and the use of cryptands. This unprecedented and operationally simple isotopic functionalization enables the reliable production of potential radiotracers for positron emission tomography, providing easy access to SuFEx radiochemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Qunchao Zhao, Jean M. Etersque, Shuiyu Lu, Sanjay Telu, Victor W. Pike
Summary: In this study, we investigated the use of aryliodonium precursors for copper-free labeling of PET tracers with fluorine-18. We found that regioisomeric F-18-fluoroarenes can be formed in certain labeling methods. The reaction between aryliodonium ylides derived from Meldrum's acid with para electron-donating groups and [F-18]-fluoride in acetonitrile produces regioisomeric F-18-fluoroarenes via a competing aryne pathway. The formation of regioisomers is decreased or absent in DMF. It is recommended to analytically check for the absence of the F-18-regioisomer in any specific PET tracer radiosynthesis using these or similar methods.