Article
Chemistry, Organic
Chunyu Han, Xianhai Tian, Lina Song, Yaowen Liu, A. Stephen K. Hashmi
Summary: A gold-catalysed cascade reaction for the synthesis of tetra-substituted furans from acceptor-substituted carbonyl compounds using hypervalent iodine(iii) reagents was described. This method involves two Au(i)/Au(iii) catalytic cycles and allows for gram-scale synthesis, with the synthesized furan product easily transformed into other related compounds. The reaction offers distinct advantages over previous methods and can tolerate a wide range of functionalities.
ORGANIC CHEMISTRY FRONTIERS
(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)
Article
Chemistry, Organic
Zhuqing Liu, Shaobin Sun, Jiang Lou
Summary: An efficient and highly regioselective reaction method has been reported for the transformation of enaminone to oxazolone via PhIO-mediated oxidation and reassembly. DFT calculations revealed the mechanism and steps of the reaction, which demonstrates high atom and step economy and the ability to form a valuable oxazolone skeleton under mild conditions.
Article
Chemistry, Multidisciplinary
Durga Prasad Hari, Guillaume Pisella, Matthew D. Wodrich, Artem Tsymbal, Farzaneh Fadaei Tirani, Rosario Scopelliti, Jerome Waser
Summary: A new oxyalkynylation/cycloaddition reaction has been reported to synthesize complex polycyclic structures under mild conditions, with high efficiency and atom economy. The obtained products can be applied as chiral ligands for metal catalysis, providing a new method for organic synthesis. Computational studies provided a first rationalization of the low activation energy for the cycloaddition reaction based on counter-intuitive favorable dispersive interactions in the transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lachlan Barwise, Jason D. Bennetts, Keith F. White, Jason L. Dutton
Summary: The synthesis and crystallographic characterization of NO2-C6H4-I(NTf2)(2) (NTf2 = bistriflimide) are reported. Experimental results demonstrate that this compound is capable of performing oxidation reactions that ArI(OTf)2 is unable to. Theoretical analysis indicates that Ar-I(NTf2)(2) is the most oxidizing compound among the known ArIL2 class of compounds, and it may also be the most oxidizing compound among the practically possible compounds in this class.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Abhaya Kumar Mishra, Romain Tessier, Durga Prasad Hari, Jerome Waser
Summary: In this study, functionalization of cysteine residues with lipophilic alkynes using amphiphilic ethynylbenziodoxolone reagents (EBXs) was successfully achieved under physiological conditions without the need for organic co-solvent or removal of oxygen. The transformation led to a significant increase of peptide lipophilicity and worked for various thiol-containing compounds and peptides of different lengths. His(6)-Cys-Ubiquitin was also alkynylated under these conditions, demonstrating the versatility of this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Biochemistry & Molecular Biology
Irina A. Mironova, Dmitrii M. Noskov, Akira Yoshimura, Mekhman S. Yusubov, Viktor V. Zhdankin
Summary: Hypervalent iodine reagents, specifically benziodoxoles, have shown improved thermal stability and synthetic versatility compared to their acyclic analogs. These reagents have found wide applications in direct arylation, alkenylation, and alkynylation reactions under mild conditions, including transition metal-free and photoredox and transition metal catalysis. They enable the synthesis of valuable and structurally diverse complex products through convenient procedures.
Article
Chemistry, Multidisciplinary
Stephanie G. E. Amos, Diana Cavalli, Franck Le Vaillant, Jerome Waser
Summary: In this study, aryl-substituted ethynylbenziodoxolone reagents were found to be directly activated by visible light irradiation, acting as oxidants and radical traps in various EBX-mediated processes. This eliminates the need for a photocatalyst, simplifying the reaction conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Huai-Ming Li, Guan-Dong Li, Jun-Yu Li, Teng Zhang
Summary: An iodine-functionalized metal-organic framework (MOF), UiO-68-I, was synthesized and showed good catalytic activity for dibromination of alkenes and alkynes. Its low catalyst loading of 1% allows for efficient recycling and recovery. Mechanistic studies suggest that UiO-68-I may accelerate the reaction by triggering the formation of molecular bromine through a radical intermediate. The activity and stability of UiO-68-I surpasses previous reports on organoiodine catalysts, highlighting the potential of iodine-functionalized MOFs as recyclable heterogeneous hypervalent iodine reagents or catalysts.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jingwei Ma, Qian Wang, Yang Sun, Eva Zhu, Xiaobao Li, Haibo Tan, Guangying Chen, Chao Zheng
Summary: In this study, we demonstrate a copper-catalyzed efficient cross-coupling reaction of aryl and alkenyl boronic acids with alkynyl-1,2-benziodoxol-3(1H)-ones to produce diaryl alkynes and enynes under mild visible light conditions. The reaction can be conducted with a catalytic amount of base or even in the absence of base. The copper catalyst used in this reaction shows excellent tolerance towards various functional groups, including aryl bromide and iodide.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Mattis Damrath, Lucien D. Caspers, Daniel Duvinage, Boris J. Nachtsheim
Summary: Two simple methods for synthesizing O- and N-bridged diaryliodonium triflates are described. Different derivatizations were applied to demonstrate their usefulness as building blocks and to gain a deeper understanding of their general reactivity.
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, Organic
Julien Borrel, Jerome Waser
Summary: In this study, a simplified synthesis method for generating Ethynylbenziodoxolones (EBXs) in one pot and directly applying them to substrate functionalization was reported. By bypassing the mandatory isolation and purification steps, this approach led to a more efficient synthesis and successful application in various transformations to obtain a diverse range of alkynylated products.
Article
Chemistry, Physical
Tian-Yu Sun, Kai Chen, Qihui Lin, Tingting You, Penggang Yin
Summary: The reaction pattern of hypervalent iodine reagents involves hypervalent twist followed by reductive elimination, and studying the mechanism of hypervalent twist can guide experiments effectively. Previous research has identified two types of hypervalent twist models, namely apical twist and equatorial twist. This study successfully identified Togni II's isomerization pathway via equatorial twist, suggesting that different hypervalent twist models should be considered to predict the correct reaction mechanisms.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
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)
