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
Biochemistry & Molecular Biology
Michael T. Shea, Gregory T. Rohde, Yulia A. Vlasenko, Pavel S. Postnikov, Mekhman S. Yusubov, Viktor V. Zhdankin, Akio Saito, Akira Yoshimura
Summary: Hypervalent iodine heterocycles are an important class of reagents in organic synthesis, and this paper presents a simple and convenient method for the synthesis of benziodazolones using readily available iodobenzamides and m-chloroperoxybenzoic acid. The new iodine heterocycles were confirmed by X-ray analysis and shown to react more efficiently than analogous benziodoxolone reagents in esterification reactions.
Article
Chemistry, Multidisciplinary
Joel Haefliger, Olga O. Sokolova, Madina Lenz, Constantin G. Daniliuc, Ryan Gilmour
Summary: The success of saturated, fluorinated heterocycles in drug discovery has led to increased research efforts in main group catalysis. By utilizing iodine(I)/iodine(III) catalysis, selective fluorinated analogs with stereocontrol have been synthesized. Furthermore, the key stereoelectronic interactions in the products have been confirmed through X-ray crystal structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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)
Correction
Chemistry, Organic
Anjali Dahiya, Ashish Kumar Sahoo, Nikita Chakraborty, Bubul Das, Bhisma K. Patel
Summary: The correction addresses some aspects of the functionalization of alkenes, alkynes, and heterocycles using hypervalent iodine reagents in a metal-free environment.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
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
Eliott Le Du, Thibaut Duhail, Matthew D. Wodrich, Rosario Scopelliti, Farzaneh Fadaei-Tirani, Elsa Anselmi, Emmanuel Magnier, Jerome Waser
Summary: This study reported the synthesis of new N-heterocyclic hypervalent iodine reagents with increased structural flexibility based on amide, amidine and sulfoximine scaffolds. The alkynylation reactions of beta-ketoesters and thiols showed variable yields, with compounds with a stronger sigma-hole reacting better. In metal-mediated transformations, the N-heterocyclic hypervalent iodine reagents gave inferior results when compared to the O-based EBX reagents.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Yuna Nishiguchi, Katsuhiko Moriyama
Summary: A new synthetic method was developed with the use of aniline-type hypervalent iodine(III) for direct cyclizations, resulting in high yields of the corresponding products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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
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)
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)
Article
Chemistry, Organic
Matteo Corrieri, Lucia De Crescentini, Fabio Mantellini, Giacomo Mari, Stefania Santeusanio, Gianfranco Favi
Summary: An oxidative cyclization reaction of electron-rich alpha-arylhydrazones using phenyliodine bis(trifluoroacetate) (PIFA) catalyst has been achieved. This metal-free and chemoselective transformation provides a practical route for the synthesis of important N-amino-1H-indoles without the need for pre-functionalization of substrates.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
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, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
