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Halogen-Controlled Synthesis of Useful Organic Molecules

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Published Papers

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

Deadline for manuscript submissions: closed (30 September 2023) | Viewed by 20400

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Special Issue Editors

Prof. Dr. Toshifumi Dohi

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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
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Cheng-Pan Zhang

E-Mail Website
Guest Editor

School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan 430070, China
Interests: the synthesis and reactivity of arylsulfonium salts; the development of novel transition-metal-catalyzed or -free fluorination and fluoroalkylation reactions

Special Issue Information

Dear Colleagues,

Halogens can be incorporated into many useful organic molecules and fine chemicals utilized in a wide range of 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 as well as the chemical reagents and catalysts for efficient halogen introductions and other synthetic transformations, such as oxidations and coupling reactions. Furthermore, unique transformations of organic substrates bearing halogen atoms have recently appeared in the literature, which includes new strategies and concepts for reaction designs controlled by the sizes and oxidation states of halogen groups. Interestingly, the number of halogens incorporated in organic molecules would sometimes alter the course of the reactions (for example, see the lactonization in Asian J. Org, Chem. 2015, 4, 1065.)

This Special Issue will highlight recent opportunities and new concepts in halogen-controlled organic synthesis (reagent and substrate controls) for their continuous development in future studies. We welcome review and original research articles associated with recent achievements in this area, for example, new strategies for organic transformation controlled by halogen groups and reagents, design of new halogen-based reagents and catalysts for selective synthesis, asymmetric transformation by chiral halogen reagents and catalysts, effective synthesis of useful halogen reagents and compound, and unique synthetic intermediate bearing halogen groups. 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 the useful organic compounds, i.e., bioactive molecules and organic materials.

Prof. Dr. Toshifumi Dohi
Prof. Dr. Cheng-Pan Zhang
Guest Editors

Manuscript Submission Information

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Keywords

Halogens
Halogen-based reagents
Hypervalent compound
New synthetic transformation
Selective transformation
Unique halogenated substrates
Bioactive compounds
Organic materials

Published Papers (5 papers)

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Research

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18 pages, 2119 KiB

Open AccessArticle

Catalyst-Free Trans-Selective Oxyiodination and Oxychlorination of Alkynes Employing N–X (Halogen) Reagents

by Jiaqiong Sun, Yunliang Guo, Jiuli Xia, Guangfan Zheng and Qian Zhang

Molecules 2023, 28(21), 7420; https://doi.org/10.3390/molecules28217420 - 3 Nov 2023

Cited by 1 | Viewed by 668

Abstract

β-halogenated enol esters and ethers are versatile building blocks in organic synthesis, which has attracted increasing attention. In this study, we report the facile trans-oxyiodination and oxychlorination of alkynes, leading to the direct construction of versatile halogenated enol esters and ethers. This transformation features an easy operation, optimal atomic economy, a strong functional group tolerance, broad substrate scope, and excellent trans-selectivity. Employing highly electrophilic bifunctional N–X (halogen) reagents was the key to achieving broad reaction generality. To our knowledge, this transformation represents the first oxyhalogenation system employing N–X (halogen) reagents as both oxylation and halogenation sources. Full article

(This article belongs to the Special Issue Halogen-Controlled Synthesis of Useful Organic Molecules)

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16 pages, 1075 KiB

Open AccessArticle

Markovnikov-Type Hydrotrifluoromethylchalcogenation of Unactivated Terminal Alkenes with [Me₄N][XCF₃] (X = S, Se) and TfOH

by Jin Shi and Cheng-Pan Zhang

Molecules 2020, 25(19), 4535; https://doi.org/10.3390/molecules25194535 - 3 Oct 2020

Cited by 10 | Viewed by 2777

Abstract

The first Markovnikov-type hydrotrifluoromethylselenolation of unactivated terminal alkenes with the readily accessible [Me₄N][SeCF₃] reagent and the superacid TfOH is reported. The reaction proceeded at room temperature under catalyst- and additive-free conditions to give the branched trifluoromethylselenolated products in good yields. This protocol is also applicable to the Markovnikov-type hydrotrifluoromethylthiolation of unactivated terminal alkenes using [Me₄N][SCF₃]/TfOH, but not to the hydrotrifluoromethoxylation with CsOCF₃/TfOH under the same conditions. The successful hydrotrifluoromethylselenolation and hydrotrifluoromethylthiolation showed simplicity and high regioselectivity, taming the sensitive ⁻XCF₃ (X = Se, S) anions with TfOH, and offered a convenient method for the straightforward synthesis of branched trifluoromethyl selenoethers and thioethers from unactivated alkenes. Full article

(This article belongs to the Special Issue Halogen-Controlled Synthesis of Useful Organic Molecules)

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Review

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44 pages, 26229 KiB

Open AccessReview

Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications

by Irina A. Mironova, Dmitrii M. Noskov, Akira Yoshimura, Mekhman S. Yusubov and Viktor V. Zhdankin

Molecules 2023, 28(5), 2136; https://doi.org/10.3390/molecules28052136 - 24 Feb 2023

Cited by 9 | Viewed by 1935

Abstract

Hypervalent iodine reagents are in high current demand due to their exceptional reactivity in oxidative transformations, as well as in diverse umpolung functionalization reactions. Cyclic hypervalent iodine compounds, known under the general name of benziodoxoles, possess improved thermal stability and synthetic versatility in comparison with their acyclic analogs. Aryl-, alkenyl-, and alkynylbenziodoxoles have recently received wide synthetic applications as efficient reagents for direct arylation, alkenylation, and alkynylation under mild reaction conditions, including transition metal-free conditions as well as photoredox and transition metal catalysis. Using these reagents, a plethora of valuable, hard-to-reach, and structurally diverse complex products can be synthesized by convenient procedures. The review covers the main aspects of the chemistry of benziodoxole-based aryl-, alkynyl-, and alkenyl- transfer reagents, including preparation and synthetic applications. Full article

(This article belongs to the Special Issue Halogen-Controlled Synthesis of Useful Organic Molecules)

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33 pages, 15917 KiB

Open AccessReview

Halogen-Induced Controllable Cyclizations as Diverse Heterocycle Synthetic Strategy

by Hideyasu China, Ravi Kumar, Kotaro Kikushima and Toshifumi Dohi

Molecules 2020, 25(24), 6007; https://doi.org/10.3390/molecules25246007 - 18 Dec 2020

Cited by 26 | Viewed by 4028

Abstract

In organic synthesis, due to their high electrophilicity and leaving group properties, halogens play pivotal roles in the activation and structural derivations of organic compounds. Recently, cyclizations induced by halogen groups that allow the production of diverse targets and the structural reorganization of organic molecules have attracted significant attention from synthetic chemists. Electrophilic halogen atoms activate unsaturated and saturated hydrocarbon moieties by generating halonium intermediates, followed by the attack of carbon-containing, nitrogen-containing, oxygen-containing, and sulfur-containing nucleophiles to give highly functionalized carbocycles and heterocycles. New transformations of halogenated organic molecules that can control the formation and stereoselectivity of the products, according to the difference in the size and number of halogen atoms, have recently been discovered. These unique cyclizations may possibly be used as efficient synthetic strategies with future advances. In this review, innovative reactions controlled by halogen groups are discussed as a new concept in the field of organic synthesis. Full article

(This article belongs to the Special Issue Halogen-Controlled Synthesis of Useful Organic Molecules)

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Figure 1

24 pages, 7061 KiB

Open AccessReview

Tetrabutylammonium Bromide (TBAB) Catalyzed Synthesis of Bioactive Heterocycles

by Bimal Krishna Banik, Bubun Banerjee, Gurpreet Kaur, Shivam Saroch and Rajat Kumar

Molecules 2020, 25(24), 5918; https://doi.org/10.3390/molecules25245918 - 14 Dec 2020

Cited by 46 | Viewed by 9853

Abstract

During the last two decades, tetrabutylammonium bromide (TBAB) has gained significant attention as an efficient metal-free homogeneous phase-transfer catalyst. A catalytic amount of TBAB is sufficient to catalyze various alkylation, oxidation, reduction, and esterification processes. It is also employed as an efficient co-catalyst for numerous coupling reactions. It has also acted as an efficient zwitterionic solvent in many organic transformations under molten conditions. In this review, we have summarized the recent developments on TBAB-catalyzed protocols for the efficient synthesis of various biologically promising heterocyclic scaffolds. Full article

(This article belongs to the Special Issue Halogen-Controlled Synthesis of Useful Organic Molecules)

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