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Hypervalent Iodine Chemistry: Promise and Prospects

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: 31 May 2025 | Viewed by 3058

Special Issue Editor


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Guest Editor
Graduate School of Pharmaceutical Sciences, Ritsumeikan University, Shiga 525-8577, Japan
Interests: hypervalent iodine chemistry and its application; oxidation; coupling; heterocycle synthesis; asymmetric synthesis
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Special Issue Information

Dear Colleagues,

Halogens can be incorporated into many useful organic molecules and fine chemicals in various scientific fields, such as natural products, biologically active compounds, and organic materials. In organic synthesis, halogen-including molecules have played distinct roles as synthetic intermediates for various transformations, chemical reagents and catalysts for efficient halogen introductions, and other synthetic transformations, such as oxidations and many bond-forming reactions.

Iodine atoms in organic compounds can easily take hypervalent forms, popularly used for oxidations and many bond-forming reactions. These hypervalent iodine reagents have become important in modern organic synthesis as greener alternatives to heavy metal oxidants because of their low toxicity, mild reactivity, high stability, easy availability and handling, ease of recovery and recyclability, etc. Recently, the field of hypervalent iodine chemistry has experienced significant growth through continuous breakthroughs in this century, evidenced by the increasing number of literature publications on the subject. Hypervalent iodine catalysis and asymmetric organocatalysis in oxidative transformations are the driving forces behind this prosperity. Using hypervalent iodine reagents in transition metal-free coupling and oxidative coupling has also significantly contributed to the field. Furthermore, new strategies and concepts for their uses in organic synthesis have appeared, which involve organic transformation controlled by hypervalent iodine groups and reagents, design of new hypervalent iodine-based reagents and catalysts, effective synthesis of useful hypervalent iodine reagents and compounds, and unique synthetic intermediate bearing hypervalent iodine groups, etc. In addition, photosensitive characteristics and unique halogen bonding interaction between hypervalent iodine atoms and heteroatom groups have become a general chemical strategy in designing photoacid generators, organic materials and pharmaceutical compounds, and new Lewis acidic catalysis.

This Special Issue will highlight recent opportunities and new concepts in hypervalent iodine reagents in organic synthesis and other applications for their continuous development in future studies. We welcome reviews and original research articles associated with recent achievements. Areas to be covered in this Special Issue may include but are not limited to the extension of the known synthetic strategy and reaction for the new construction of organic molecules and for application to useful organic compounds, i.e., bioactive molecules and organic materials.

Prof. Dr. Toshifumi Dohi
Guest Editor

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Keywords

  • hypervalent compound
  • iodine
  • new reagent and catalyst
  • new synthetic transformation
  • synthetic application
  • the hypervalent iodine-bearing hybrid molecule

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Published Papers (2 papers)

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Research

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32 pages, 1722 KiB  
Article
Synthesis of Unsymmetrical Urea Derivatives via PhI(OAc)2 and Application in Late-Stage Drug Functionalization
by Subban Kathiravan, Prakriti Dhillon, Tianshu Zhang and Ian A. Nicholls
Molecules 2024, 29(23), 5669; https://doi.org/10.3390/molecules29235669 - 29 Nov 2024
Viewed by 1618
Abstract
Unsymmetrical urea derivatives are essential structural motifs in a wide array of biologically significant compounds. Despite the well-established methods for synthesizing symmetrical ureas, efficient strategies for the synthesis of unsymmetrical urea derivatives remain limited. In this study, we present a novel approach for [...] Read more.
Unsymmetrical urea derivatives are essential structural motifs in a wide array of biologically significant compounds. Despite the well-established methods for synthesizing symmetrical ureas, efficient strategies for the synthesis of unsymmetrical urea derivatives remain limited. In this study, we present a novel approach for the synthesis of unsymmetrical urea derivatives through the coupling of amides and amines. Utilizing hypervalent iodine reagent PhI(OAc)2 as a coupling mediator, this method circumvents the need for metal catalysts, high temperatures, and inert atmosphere. The reaction proceeds under mild conditions and demonstrates broad substrate scope, including various primary and secondary amines and primary benzamides. This protocol not only offers a practical and versatile route for synthesizing unsymmetrical ureas but also shows significant potential for the late-stage functionalization of complex molecules in drug development. Full article
(This article belongs to the Special Issue Hypervalent Iodine Chemistry: Promise and Prospects)
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Review

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28 pages, 10012 KiB  
Review
Iodine(III)-Containing Reagents in Photo-Assisted and Photo-Catalyzed Organic Synthesis
by Jaime G. Ibarra-Gutiérrez, Luis A. Segura-Quezada, Edson D. Hernández-Velázquez, Ana K. García-Dueñas, José A. Millán-Cortés, Kevin Mondragón-Hernández, Luz K. Miranda-Navarrete, Evelyn M. Valtierra-Camarena, Steffi Y. Yebra-Rivera, Omar E. Alférez-Carmona, Oliver E. Ávalos-Otero, Rubén Chávez-Rivera, Claudia de León-Solís, Rafael Ortíz-Alvarado and César R. Solorio-Alvarado
Molecules 2025, 30(4), 784; https://doi.org/10.3390/molecules30040784 - 8 Feb 2025
Viewed by 883
Abstract
Iodine(III) reagents have become a highly relevant tool in organic synthesis due to their great versatility as strong but green oxidants. Several transformations involving cyclizations as well as functionalization of different organic cores have been broadly described and reviewed. Herein, the participation of [...] Read more.
Iodine(III) reagents have become a highly relevant tool in organic synthesis due to their great versatility as strong but green oxidants. Several transformations involving cyclizations as well as functionalization of different organic cores have been broadly described and reviewed. Herein, the participation of these reagents in photochemical transformations exclusively by direct irradition or in photoredox cycles using some transition metals, will be briefly described as well as some plausible further transformations that potentially can be developed. Full article
(This article belongs to the Special Issue Hypervalent Iodine Chemistry: Promise and Prospects)
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