Article
Chemistry, Applied
Yingbo Shao, Zhiyuan Ren, Chenfengtao Zheng, Xiao-Song Xue
Summary: In this study, we computationally investigated the mechanism and origin of the reactivity difference between N-triflylimino-lambda(3)-iodane and N-triflylimino-lambda(3)-bromane in C-H amination and alkene aziridination. Our calculations revealed that the formation of a free nitrene intermediate is the preferred mechanism for C-H amination, while a concerted reaction mechanism is involved in the alkene aziridination. The higher reactivity of N-triflylimino-lambda(3)-bromane compared to N-triflylimino-lambda(3)-iodane can mainly be attributed to the better nucleofugality of the bromanyl moiety, which can be characterized by the strength of the I-N and Br-N bonds. The impact of solvent polarity on the reactivity of N-triflylimino-lambda(3)-bromane as a nitrene precursor is also discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jessica C. Bieniek, Boris Mashtakov, Dieter Schollmeyer, Siegfried R. Waldvogel
Summary: This study presents an electrocatalytic method using hypervalent iodine(III) as a mediator to synthesize 1H-N-aryl-3,4-dihydroquinolin-2-ones by C-N bond formation. The method features a low catalyst loading, recycling of the solvent, and is a sustainable alternative to conventional approaches.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
Bing Zu, Jie Ke, Yonghong Guo, Chuan He
Summary: Anodic oxidation enables the synthesis and derivatization of hypervalent iodine(III) reagents from aryl iodides under mild electrochemical conditions. This method offers a straightforward and sustainable approach by using only electrons as the oxidation reagents, thus avoiding the use of expensive or hazardous chemical oxidants.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Julian Spils, Thomas Wirth, Boris J. Nachtsheim
Summary: We present a multi-step continuous-flow approach to produce six-membered diaryliodonium salts, with improved scalability and atom economy compared to existing batch methods. Benzyl acetates serve as readily available and cost-effective starting materials in this two-step procedure. An acid-catalyzed Friedel-Crafts alkylation followed by an anodic oxidative cyclization results in a defined set of cyclic iodonium salts, with yield depending on the substrate characteristics.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shun Sunagawa, Fumiya Morisaki, Takafumi Baba, Akira Tsubouchi, Akira Yoshimura, Kazunori Miyamoto, Masanobu Uchiyama, Akio Saito
Summary: In this study, the imidation of phosphines and a-amidation of 1,3-dicarbonyl compounds were achieved using N-triflylimino-lambda(3)-iodane, which was generated in situ from iodosylarene and triflylamide without any other additives. Additionally, the a-amidation of 1,3-dicarbonyl compounds was catalyzed by the imino-lambda(3)-iodane generated from an iodoarene precatalyst with oxone and triflylamide, representing the first method catalyzed by imino-lambda(3)-iodane.
Article
Chemistry, Multidisciplinary
Qing-Qing Han, De-Mao Chen, Zu-Li Wang, Yuan-Yuan Sun, Shao-Hui Yang, Jing-Cheng Song, Dao-Qing Dong
Summary: An efficient and facile method for C-H amination of quinoxalinones with heteroaromatic amines under metal-free conditions has been described. The desired products with various groups were obtained with moderate to high yields in the presence of hypervalent PIDA reagent.
CHINESE CHEMICAL LETTERS
(2021)
Article
Biochemistry & Molecular Biology
Chunngai Hui, Andrey P. Antonchick
Summary: A concise synthesis of piperarborenine B is reported, which involves multiple steps including organocatalytic electrophilic amination and stereospecific oxidative ring contraction. The synthesis was achieved without the use of transition metals, directing groups or protecting groups, providing a novel strategy for the preparation of a non-symmetrical cyclobutane core.
BIOORGANIC & MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Feng Liu, Jie Dai, Xu Cheng
Summary: A protocol for electrochemical aziridination of electron-deficient alkenes using phthalhydrazide as a nitrogen source was reported. The reaction can be conducted in an undivided cell, and in-situ generated nitrogen sources are suggested for the stepwise aziridination, which can be applied to various compounds to synthesize N-containing molecules.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lipiao Bao, Baolin Zhao, Bowen Yang, Marcus Halik, Frank Hauke, Andreas Hirsch
Summary: A series of hypervalent iodine compounds have been reported as highly efficient for diversified graphene patterning, generating reactive radicals for controlled chlorination, hydroxylation, and trifluoromethylation. The highly functionalized graphene nanoarchitectures allow for reversible attachment of functional entities with full control over stored chemical information. This work provides an exciting approach for target 2D functionalization and modulation of graphene using suitable hypervalent iodine compounds.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Kumar Bhaskar Pal, Ester Maria Di Tommaso, A. Ken Inge, Berit Olofsson
Summary: We report an efficient radical-mediated C-C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C-C bond formation is stereospecific and proceeds through a concerted radical coupling transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Organic
Thibaut Duhail, Jorna Kalim, Jerome Marrot, Bruce Pegot, Emmanuel Magnier, Elsa Anselmi
Summary: This study describes hypervalent iodine compounds with specific ligands, investigating the influence of these groups on the stability of cyclic structure and highlighting the crucial role of the trifluoromethyl chain as an efficient ligand. The structure and reactivity of the new skeletons are discussed in detail.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jorna Kalim, Thibaut Duhail, Ewa Pietrasiak, Elsa Anselmi, Emmanuel Magnier, Antonio Togni
Summary: A study has discovered a method for direct trifluoromethylation of various aliphatic alcohols using a hypervalent iodosulfoximine reagent, resulting in the efficient synthesis of corresponding ethers.
CHEMISTRY-A EUROPEAN JOURNAL
(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)
Article
Chemistry, Inorganic & Nuclear
Sanjay Gaire, Briana R. Schrage, Victor N. Nemykin, Christopher J. Ziegler
Summary: The semihemiporphyrazines are a class of ligands comprised of a heterocycle ring and an isoindoline unit linked through a bridging nitrogen atom. Altering the ligand and the axial position at the metal can change the properties of the complexes, including structure, tautomerization, and chirality. Modifying the semihemiporphyrazine also affects the electronic structure of the resulting Re(CO)(3) complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Briana R. Schrage, Eugeny Ermilov, Victor N. Nemykin
Summary: The formation and deactivation of charge-separated state was investigated in a series of compounds using transient absorption spectra. The lifetime of the charge-separated state was nearly constant for all compounds and independent of the central ion and solvent. A minor long-lived component was observed in polar solvent.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Dustin E. Nevonen, Laura S. Ferch, Briana R. Schrage, Victor N. Nemykin
Summary: This study investigates the correlation between the position of the metal-to-ligand charge-transfer (MLCT) band and the electrochemical EL scale values of axial ligands in low-spin iron(II) phthalocyanine complexes using experimental and theoretical methods. The results show that the first degenerate MLCT band is dominated by a single-electron excitation and there is a small energy gap for orbital splitting and closeness of transitions. Additional charge-transfer transitions were observed for complexes with phosphine axial ligands.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuriy Zatsikha, Liliya Shamova, Michael Shepit, Steven M. Berry, Fabrice Thomas, David E. Herbert, Johan van Lierop, Victor N. Nemykin
Summary: The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm has been a long-standing challenge in the chemistry of functional dyes. In this study, a series of unprecedented stable neutral nickel(II) and copper(II) complexes were prepared, in which the organic chromophore exists in the radical-anion state. The new stable radicals have an intense absorption at around 1300 nm and can be oxidized or reduced to different compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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
Biochemistry & Molecular Biology
Irina A. Mironova, Valentine G. Nenajdenko, Pavel S. Postnikov, Akio Saito, Mekhman S. Yusubov, Akira Yoshimura
Summary: The intramolecular oxidative cycloaddition reaction of alkyne- or alkene-tethered aldoximes was efficiently catalyzed by hypervalent iodine(III) species, resulting in the formation of polycyclic isoxazole derivatives with yields of up to 94%. The structure of the products was confirmed through various methods, including X-ray crystallography. Mechanistic studies revealed the critical role of hydroxy(aryl)iodonium tosylate as a precatalyst, which is formed from 2-iodobenzoic acid and m-chloroperoxybenzoic acid in the presence of a catalytic amount of p-toluenesulfonic acid.
Article
Chemistry, Organic
Shun Sunagawa, Fumiya Morisaki, Takafumi Baba, Akira Tsubouchi, Akira Yoshimura, Kazunori Miyamoto, Masanobu Uchiyama, Akio Saito
Summary: In this study, the imidation of phosphines and a-amidation of 1,3-dicarbonyl compounds were achieved using N-triflylimino-lambda(3)-iodane, which was generated in situ from iodosylarene and triflylamide without any other additives. Additionally, the a-amidation of 1,3-dicarbonyl compounds was catalyzed by the imino-lambda(3)-iodane generated from an iodoarene precatalyst with oxone and triflylamide, representing the first method catalyzed by imino-lambda(3)-iodane.
Article
Chemistry, Inorganic & Nuclear
Briana R. Schrage, Wen Zhou, Laurel A. Harrison, Dustin E. Nevonen, John R. Thompson, Kathleen E. Prosser, Charles J. Walsby, Christopher J. Ziegler, Daniel B. Leznoff, Victor N. Nemykin
Summary: This article reports on the properties of the reduction of iron(II) phthalocyanine and the resulting species. The study found that the reduced species have a purple/red color and possess a single unpaired electron with a magnetic moment. Additionally, through experiments and calculations, the spectral characteristics of these species were confirmed, resolving previous controversies.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Victor N. Nemykin, Briana R. Schrage, Dustin E. Nevonen, Laurel A. Harrison, Kelly M. E. Newman, Vinod K. Paidi, Johan van Lierop
Summary: The properties of ((PcFe)-Fe-(tBu)4)(2)O and ((PyPcFe)-Fe-(tBu)4)(2)O complexes were investigated using various spectroscopic, electrochemical, and theoretical methods. Different isomers were observed for ((PcFe)-Fe-(tBu)4)(2)O in the solid state and in solution. The UV-vis spectra and MCD spectra of the complexes were analyzed using exciton coupling theory and TDDFT calculations.
INORGANIC CHEMISTRY
(2023)
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, Physical
Sayantan Bhattacharya, Dustin E. Nevonen, Alexander J. Auty, Arthur Graf, Martin Appleby, Nivedita Chaudhri, Dimitri Chekulaev, Christian Bruckner, Adrien A. P. Chauvet, Victor N. Nemykin
Summary: The introduction of three ss-oxosubstituents to octaethylporphyrin generates the aromatic trioxopyrrocorphin chromophore. Photophysical characteristics of these chromophores, including UV-vis and magnetic circular dichroism spectra, conform to the Gouterman model of porphyrinoid optical spectra. The study also reveals that the introduction of ss-oxo functionalities tunes the photophysical properties of porphyrinoids, increasing intersystem crossing rate and shortening triplet state lifetime.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Dustin E. Nevonen, Jenna C. Wagner, Christian Bru''ckner, Christopher J. Ziegler, Victor N. Nemykin
Summary: We systematically investigated Ag(II) and Ag(III) complexes of porphyrins and their analogues using UV-vis magnetic circular dichroism (MCD) spectroscopies and theoretical calculations. Ag(II) and Ag(III) octaethyl- and tetraarylporphyrins showed a typical sign sequence in the Q-band region of their MCD spectra, indicating an HOMO > LUMO relationship. However, Ag(II) complexes of β,β’-pyrrole-modified porphyrins and Ag(III) corroles showed reverse features in the MCD spectra, with an HOMO < LUMO relationship. The Ag(III) complex of N-confused porphyrin exhibited an HOMO > LUMO relationship in the neutral state and an HOMO < LUMO relationship in the protonated form.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Inorganic & Nuclear
Christopher J. Ziegler, Victor N. Nemykin
Summary: This Frontier article discusses the influence of axial ligands on the spectroscopic and redox properties of iron(ii) phthalocyanines, covering topics such as oxidation and reduction processes, charge transfer transitions, and the role of axial ligands in binding.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Sayantan Bhattacharya, Dustin E. Nevonen, Alexander J. Auty, Arthur Graf, Martin Appleby, Nivedita Chaudhri, Dimitri Chekulaev, Christian Bruckner, Adrien A. P. Chauvet, Victor N. Nemykin
Summary: The introduction of three ss-oxosubstituents to octaethylporphyrin generates the trioxopyrrocorphin chromophore, which possesses considerable aromatic character. This study explores the photophysical characteristics of these unusual chromophores and reveals that the ss-oxo substitutions can tune the photophysical properties of porphyrinoids and enhance singlet oxygen yield.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Austen Moss, Dustin E. Nevonen, Yi Hu, Vladimir N. Nesterov, Victor N. Nemykin, Hong Wang
Summary: In this study, unsymmetric pentacenequinone-fused and pentacene-fused porphyrins were designed and synthesized, showing unusual optical and electronic properties different from typical porphyrins. The complex absorption and MCD spectra of these molecular systems were analyzed using MCD, DFT, and TDDFT calculations, suggesting the existence of multiple charge transfer states. The traditional Gouterman's four-orbital model was found to be contradictory to the theoretical and experimental data, and a new interpretation method based on 2+4 and 3+3 active spaces was proposed. Furthermore, the pentacene-fused porphyrins exhibited exceptional ability in accommodating positive charges and showed a pronounced metal effect. This work provides important information for guiding new material designs.
ACS PHYSICAL CHEMISTRY AU
(2022)
