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
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
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, Multidisciplinary
Darius Vrubliauskas, Benjamin M. Gross, Christopher D. Vanderwal
Summary: In this article, the tolerance of Co-catalyzed MHAT-initiated radical bicyclizations towards oxidation at virtually every position in the substrate, oftentimes in unprotected form, is demonstrated. The functional groups in the substrate can also contribute to high levels of stereochemical control in these complexity-generating transformations. Furthermore, the utility of these reactions in the synthesis of three aromatic abietane diterpenoids is documented.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
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)
Review
Chemistry, Multidisciplinary
Ravi Kumar, Fateh V. Singh, Naoko Takenaga, Toshifumi Dohi
Summary: The review focuses on asymmetric oxidative dearomatization reactions involving hypervalent iodine compounds, summarizing asymmetric intra- and intermolecular dearomatization reactions using chiral hypervalent iodine reagents/catalysts as well as hypervalent iodine-mediated dearomatization reactions followed by desymmetrization.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Huaiyuan Zhang, Thomas Wirth
Summary: Xanthene derivatives derived from BINOL have wide applications in various fields such as medicine, fluorescent probes, dyes, and food additives. Researchers have developed synthetic methods for preparing the oxidized products of BINOL using different methods. One-pot reactions of BINOLs, reagents, and nucleophiles have also been investigated, resulting in high-yielding products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Min Zhang, Qiang Li, Jin-Hong Lin, Ji-Chang Xiao
Summary: Due to its unique electronic properties, the difluoromethylene group (CF2) has been used in the design of biologically active molecules. The synthesis of alpha,alpha-difluoro-gamma-lactones has gained attention due to their potential unexpected biological activities. Traditional synthetic methods are tedious, but a new method using BrCF2CO2K under photoredox catalysis has been developed, which is efficient and atom economy.
CHINESE JOURNAL OF CHEMISTRY
(2023)
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.
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
Materials Science, Ceramics
Longfei Zhang, Yiguang Jiang, Zaiyang Wang, Feng Guan, Yanchao Li, Xinqiang Yuan, Long Zhang
Summary: This study comprehensively evaluated the thermal properties, microstructure, crystal phase behaviors, and optical and luminescent properties of high-temperature FIG. It was found that high temperatures could lead to the fracture of bridge bonds between some [InF6](3-) octahedrons in FIG, causing glass structural instability and increasing the tendency of devitrification.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2022)
Article
Chemistry, Physical
Junjie Yang, Yung-Yin Chan, Weida Feng, Ying-Lung Steve Tse, Ying-Yeung Yeung
Summary: Electrophilic halogenation reactions are commonly used in various areas. N-Haloamides are frequently employed as halogen sources, but their activation is often achieved with Lewis basic chalcogens as catalysts. However, the resulting intermediate is sensitive to moisture and nucleophiles, limiting its compatibility in some reactions. This study introduces a highly efficient catalytic halogenation protocol using phenyl selenium with ortho-substituted carboxylic acid as the catalyst, which demonstrates improved stability and applicability in various electrophilic functionalization reactions.
Article
Chemistry, Multidisciplinary
Erika Linde, Berit Olofsson
Summary: The diarylation and skeletal diversification of unstrained cyclic amines was explored to expand and modify their properties. A novel class of amino-substituted diaryliodonium salts was synthesized from cyclic amines and converted to highly functionalized diarylamines through a one-pot N-arylation/ring opening reaction. This strategy proved efficient in the late-stage functionalization of natural products and pharmaceuticals, and provided a wide variety of complex diarylamines. The method involves the introduction of two different aryl groups and the retention of an iodo-substituent, allowing for downfield diversification of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Wei Wu, Shunli Wen, Xinyu Zhang, Qi Lin, Zhiqiang Weng
Summary: A highly efficient and regioselective synthesis of highly substituted 2-trifluoromethyl pyrrole derivatives is reported via a silver-catalyzed cyclization of vinyl azides with ethyl 4,4,4-trifluoro-3-oxobutanoate. Various types of alpha-(heteo)aryl, alkyl, alpha-aryl, and alpha,beta-disubstituted vinyl azides can participate in this transformation. The proposed reaction mechanism involves the addition of in situ generated 2H-azirine to the diketone species, followed by intramolecular addition, N-C-1 cleavage, and elimination.
