Article
Chemistry, Multidisciplinary
Jiang Nan, Xin Ren, Qiang Yan, Shilei Liu, Jing Wang, Yangmin Ma, Michal Szostak
Summary: A novel hypervalent iodine-induced twofold oxidative coupling of amines with amides and thioamides has been established, which chemoselectively assembles oxazoles and thiazoles. The mechanism involves the generation of ureas and thioureas as intermediates. These findings open up new avenues for exploring oxidative bond chemistry of amides and thioamides.
Review
Chemistry, Multidisciplinary
Samata E. Shetgaonkar, Aleena Raju, Hideyasu China, Naoko Takenaga, Toshifumi Dohi, Fateh V. Singh
Summary: Transition metal-catalyzed direct oxidative coupling reactions via C-H bond activation have become a convenient strategy for constructing complex molecules in organic synthesis. By directly transforming C-H bonds into carbon-carbon and carbon-heteroatom bonds, these reactions offer a more efficient alternative to traditional cross-coupling reactions. Hypervalent iodine compounds, with their excellent oxidizing nature and versatile reactivity, have emerged as mainstream reagents in this field.
FRONTIERS IN CHEMISTRY
(2022)
Article
Agricultural Engineering
Qin Chen, Chang Peng, Wujun Liu, Siyang Ning, Gang Hu, Zongbao K. Zhao, Haibo Xie
Summary: This study utilized a hypervalent iodine reagent to achieve the oxidative coupling of Kraft lignin, resulting in improved properties and enhanced adsorptive features. Adsorption kinetics, isotherms, and structural changes were investigated, showing promising results for valorizing lignin-based materials.
INDUSTRIAL CROPS AND PRODUCTS
(2022)
Article
Chemistry, Multidisciplinary
Masaki Fujie, Kyohei Mizufune, Yoshihiro Nishimoto, Makoto Yasuda
Summary: Proximal aryl C-H sulfonyloxylation and acetoxylation on 2-iodo-1,1-biphenyl structures have been achieved using λ3-iodane as a catalyst. The key step in this reaction involves intramolecular electron transfer between cationic I(III) and proximal 2-Ar groups in 2-arylphenyl-lambda 3-iodanes, leading to the generation of an iodanyl radical intermediate with a radical cationic Ar moiety. This intermediate then undergoes nucleophilic addition of acetate or sulfonate. The proposed mechanism is supported by electron spin resonance experiments. A 2-benzyl-iodobenzene structure is also compatible with this reaction system.
Article
Chemistry, Multidisciplinary
Shengtai Hou, Jialu Xu, Junjie Wang, Hongjie Wang, Pengfei Zhang
Summary: In this study, various azo-based polymers were synthesized using mechanochemical oxidative metal-free systems. By enhancing steric hindrance, explosions were effectively prevented, and a facile and innovative solid-phase synthesis method was developed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Vijayalakshmi Ramavath, Bapurao D. Rupanawar, Satish G. More, Ajay H. Bansode, Gurunath Suryavanshi
Summary: The hypervalent iodine(iii) induced oxidative olefination using 2C-Wittig reagents provides an efficient method to synthesize alpha,beta-unsaturated esters with mild reaction conditions, high yields, and good (E) selectivity. The reaction has been successfully scaled up for gram-scale synthesis.
NEW JOURNAL OF CHEMISTRY
(2021)
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, Applied
Stanislav A. Paveliev, Oleg O. Segida, Oleg Bityukov, Hai-Tao Tang, Ying-Ming Pan, Gennady Nikishin, Alexander O. Terent'ev
Summary: In this study, the electrochemical intramolecular cross-dehydrogenative C(sp(2))-H/N-H coupling of alpha,beta-unsaturated hydrazones resulting in substituted pyrazoles has been discovered. This process is catalyzed by hypervalent iodine species generated in situ through anodic oxidation of aryl iodide in fluorinated alcohol media. The formation of hypervalent iodine compound and its key role in the construction of a new C-N bond were confirmed with CV and NMR experiments. A wide range of substituted pyrazoles were obtained with yields ranging from 46% to 88%.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Xiaotao Zhang, Miaomiao Liu, Hao Ge, Zhipeng Zhang
Summary: A class of confined chiral hypervalent iodines, designed by incorporating two sterically demanding BINOL-derived units, demonstrated good-to-excellent enantioselectivities in the α-oxysulfonylation of ketones (up to 97.5:2.5 er) and the oxidative cyclization of 5-oxo-5-arylpentanoic acids to γ-butyrolactones (up to 98:2 er), showing the effectiveness of this catalyst design strategy.
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
Quan-Bing Wang, Shi Tang, Ying-Jie Wang, Yue Yuan, Tieqiao Chen, Ai-Qun Jia
Summary: The PIDA mediated intramolecular oxidative C-N coupling and subsequent detosylative aromatization allowed for the synthesis of valuable indolo[2,3-b]quinoline derivatives, providing an efficient method for their preparation.
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, Multidisciplinary
Victor Garcia-Vazquez, Alba Carretero Cerdan, Amparo Sanz-Marco, Enrique Gomez-Bengoa, Belen Martin-Matute
Summary: This paper introduces a novel umpolung protocol for the functionalization of silyl enol ethers and 1,3-dicarbonyl compounds using a specific brominated compound as a key reagent. The mechanism of the reaction is studied experimentally and by DFT, proposing the formation of an unusual enolonium intermediate with a halogen-bonded bromide.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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)
Review
Chemistry, Organic
Kotaro Kikushima, Ravi Kumar, Toshifumi Dohi
Summary: The use of [F-18]-labeled drugs and radioligands is common in PET radiopharmaceuticals for clinical and preclinical research. Various methods for introducing [F-18]fluorine into complex molecules through fluorination reactions have been reported. Recent advances in [F-18]-fluorination using aryliodonium(III) compounds are highlighted in this study.
MINI-REVIEWS IN ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Kotaro Kikushima, Haruka Koyama, Kazuki Kodama, Toshifumi Dohi
Summary: The study demonstrates metal-free synthesis of monosubstituted aromatic compounds via nucleophilic aromatic substitution reactions, resulting in functionalized PTH derivatives through two-step reactions, some of which show potential application as photocatalysts for carbon-halogen bond reduction.
Article
Biochemistry & Molecular Biology
Hideyasu China, Nami Kageyama, Hotaka Yatabe, Naoko Takenaga, Toshifumi Dohi
Summary: A convenient method for preparing nonexplosive cyclic hypervalent iodine(III) oxidants using Oxone(R) in aqueous solution at room temperature has been reported. The obtained 2-iodosobenzoic acids (IBAs) can serve as precursors for other cyclic organoiodine(III) derivatives, providing excellent yields without contamination by hazardous pentavalent iodine(III) compounds.
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)
Review
Chemistry, Organic
Kotaro Kikushima, Elghareeb E. Elboray, J. Oscar C. Jimenez-Halla, Cesar R. Solorio-Alvarado, Toshifumi Dohi
Summary: This review summarizes the double functionalization of carbon-iodine(iii) and ortho carbon-hydrogen bonds using diaryliodonium(iii) salts, which has significant application value in molecular synthesis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Kotaro Kikushima, Naoki Miyamoto, Kazuma Watanabe, Daichi Koseki, Yasuyuki Kita, Toshifumi Dohi
Summary: High reactivity of trimethoxyphenyl (TMP)-iodonium(III) acetate was achieved for phenol O-arylation. The cooperation of TMP ligand and acetate anion enhances the electrophilic reactivity towards phenol oxygen atoms. This ligand- and counterion-assisted strategy shows high applicability with tolerance towards various functional groups.
Review
Chemistry, Organic
Rimi, Sakshi Soni, Bhawna Uttam, Hideyasu China, Toshifumi Dohi, Viktor V. Zhdankin, Ravi Kumar
SYNTHESIS-STUTTGART
(2022)
Review
Biochemistry & Molecular Biology
Samata E. Shetgaonkar, Ritu Mamgain, Kotaro Kikushima, Toshifumi Dohi, Fateh V. Singh
Summary: The chemistry of polyvalent iodine compounds has attracted researchers' interest due to their role as important and flexible reagents in synthetic organic chemistry, leading to the production of various useful organic molecules. These chemicals have potential applications in functionalization processes due to their non-toxic and environmentally friendly properties. Recent research has focused on the use of hypervalent iodine reagents in palladium-catalyzed transformations, particularly in C-H bond functionalization. The article provides a detailed review of the recent advances in palladium-catalyzed oxidative cross-coupling reactions employing hypervalent iodine reagents.
Article
Chemistry, Organic
Koji Morimoto, Kana Yanase, Kentaro Toda, Hitoshi Takeuchi, Toshifumi Dohi, Yasuyuki Kita
Summary: In this study, a metal-free cross-dehydrogenative coupling of phenols and anilines with phenothiazines was achieved using hypervalent iodine reagents. The method allowed selective amination products to be obtained under mild conditions. The reaction proceeded efficiently at previously unreported 20 degrees C for aniline amination.
Article
Chemistry, Organic
Kotaro Kikushima, Aki Morita, Elghareeb E. Elboray, Taeho Bae, Naoki Miyamoto, Yasuyuki Kita, Toshifumi Dohi
Summary: TMP-iodonium(III) acetate serves as an efficient arylation reagent for N,O-protected hydroxylamines, generating aniline derivatives without the need for transition metal catalysts. The amination reaction is compatible with various protecting groups, producing versatile synthetic intermediates for functional organic molecules.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Kotaro Kikushima, Kohei Yamada, Narumi Umekawa, Natsumi Yoshio, Yasuyuki Kita, Toshifumi Dohi
Summary: Catalyst-free access to aryldifluoromethyl ketones has been achieved through decarboxylative arylation of alpha,alpha-difluoro-beta-ketoacid salts using diaryliodonium(iii) salts. The products were successfully transformed into the corresponding esters, amides, and difluoromethyl compounds. This strategy provides access to fluorine-containing drugs, thus contributing to drug design.
Article
Chemistry, Applied
Elghareeb E. Elboray, Taeho Bae, Kotaro Kikushima, Yasuyuki Kita, Toshifumi Dohi
Summary: We developed a metal catalyst-free protocol for O-arylation of benzamide hydroxamate esters. By varying the electronic and/or steric properties of the diaryliodonium salt and/or the substrate, the chemoselective O- versus N-arylation of the amides was controlled. The O-arylation reaction showed preference for sterically and electronically diverse substrates. This study demonstrates the possibility of substituent- and reagent-controlled chemoselectivity with diaryliodonium salts and may draw interest in the field of hypervalent iodine chemistry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Mohammed F. F. Radwan, Elghareeb E. E. Elboray, Hemat M. M. Dardeer, Yusuke Kobayashi, Takumi Furuta, Shohei Hamada, Toshifumi Dohi, Moustafa F. F. Aly
Summary: 1,3-Dipolar cycloaddition through in situ generation of azomethine ylide provides a straightforward and critically important sustainable approach for access to diverse pyrrolidine chemical space. Metal-free AcOH-activated 1,3-dipolar cycloaddition protocol was developed to synthesize uncommon pyrrolidine cycloadducts with excellent diastereoselectivity. The reaction mechanism and the key role of AcOH were supported by experimental, theoretical and spectroscopic studies.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Biochemistry & Molecular Biology
Samata E. Shetgaonkar, Subhiksha Jothish, Toshifumi Dohi, Fateh V. Singh
Summary: The chemistry of hypervalent iodine reagents has become valuable due to their reactivity under mild reaction conditions and resemblance to transition metals. These environmentally friendly reagents are suitable for Green Chemistry. Iodine(V) reagents, such as IBX and DMP, have been used as oxidants in organic synthesis either stoichiometrically or catalytically. This review article describes various oxidation reactions induced by iodine(V) reagents reported in the past decade.
Review
Chemistry, Organic
Luis A. Segura-Quezada, Karina R. Torres-Carbajal, Kevin A. Juarez-Ornelas, Angel J. Alonso-Castro, Rafael Ortiz-Alvarado, Toshifumi Dohi, Cesar R. Solorio-Alvarado
Summary: Iodine (III) reagents, with their characteristics of safety, environmental friendliness, and ease of use, have become important alternatives in organic synthesis. They have been widely used in the functionalization of various aromatic cores, introducing multiple functional groups. Furthermore, iodine (III) reagents have significant applications in metal-free arylation reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
