Article
Chemistry, Multidisciplinary
Michael Schaefer, Timo Stuenkel, Constantin G. Daniliuc, Ryan Gilmour
Summary: The regio- and enantioselective intermolecular vicinal fluoroamination of alpha-trifluoromethyl styrenes has been achieved through enantioselective I-I/I-III catalysis, providing facile access to tertiary benzylic stereocenters bearing both CF3 and F groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nagarajan Ramkumar, Larisa Baumane, Dzintars Zacs, Janis Veliks
Summary: A simple process for the oxy-monofluoromethylation of alkenes is presented. The use of visible-light copper(I) photoredox catalysis, in combination with an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands, enables the synthesis of gamma-fluoro-acetates from various olefinic substrates under mild conditions. The study also demonstrates its applications in late-stage diversification of complex molecules, amino acids, and the synthesis of fluoromethylated heterocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
You-Jie Yu, Joel Haefliger, Zi-Xuan Wang, Constantin G. Daniliuc, Ryan Gilmour
Summary: A main-group catalysis-based strategy for accessing 8-membered carbocycles via direct carbofunctionalization of 2-phenethyl-substituted 1,3-dienes is presented. By utilizing an I(I)/I(III) catalysis cycle, densely functionalized, fluorinated benzocyclooctenes can be synthesized in a straightforward manner. The process, which involves modulation of the oxidation/activation regime and the external nucleophile, has been extended to enable the cyclization with allylic C-O, C-N, and C-C bond formation (>30 examples).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Organic
Victor Martin-Heras, Constantin G. Daniliuc, Ryan Gilmour
Summary: The heptafluoroisopropyl group plays an important role in contemporary agrochemistry, with I(I)/I(III) catalysis used to achieve direct difluorination of aryl compounds. This method improves synthetic efficiency and compatibility with various functional groups, with potential applications in functional molecule design.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Haifa Alharbi, Mohamed Elsherbini, Jihan Qurban, Thomas Wirth
Summary: A library of novel C-N axially chiral iodoarenes was successfully synthesized from commercially available aniline derivatives in a three-step synthesis. These novel chiral iodoarenes were found to have potential as organocatalysts for stereoselective oxidative transformations, with good stereochemical control observed in the oxidation of propiophenone.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Shuang Wu, Yiyun Chen
Summary: In this study, we demonstrate the alpha-C-H acyloxylation of sulfides and disulfides using hypervalent iodine(III) reagents and photoredox catalysis. Methoxylbenziodoxole derivatives act as hydrogen atom transfer agents, mild oxidants, and acyloxylation sources in the reaction. External nucleophiles can also be introduced to the alpha-C-H of sulfides. This reaction is applicable to various aryl and alkyl sulfides, including methionine peptide derivatives. Disulfides can be used for the first time with excellent chemoselectivity and functional group compatibility.
ADVANCED SYNTHESIS & CATALYSIS
(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, Applied
Maxime Denis, Samuel Blais, Sylvain Canesi
Summary: A stereoselective synthesis of isolycoricidine, a natural product belonging to the Amaryllidaceae alkaloids family, was achieved. The study also conducted a synthetic investigation on the main core of lycoricidine, resulting in the formation of analogues and a diastereomer of dihydrolycoricidine. The research utilized various strategies including oxidative phenol dearomatization, stereoselective Heck process, selective dihydroxylation, stereoselective reductions, and oxidative retro-Michael procedure as an amine-deprotecting group strategy. In addition, the study highlighted the usefulness of hypervalent iodines in total synthesis of natural products.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Tino P. Golub, Ayham H. Abazid, Boris J. Nachtsheim, Christian Merten
Summary: In this study, vibrational circular dichroism (VCD) spectroscopy was used as an experimental technique to verify DFT-calculated chiral iodane structures. The research revealed that an undescribed cationic chiral iodane was the most common intermediate under oxidative conditions, with significant intramolecular interactions and no significant interactions with potential anionic ligands. Aggregation of the substrates resulted in the formation of a non-coordinating anionic hydrogen bonded complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sabrina Giofre, Letizia Molteni, Donatella Nava, Leonardo Lo Presti, Egle Maria Beccalli
Summary: Excellent enantio- and diastereoselectivity can be achieved in the oxidative Pd-catalyzed dioxygenation of (aza-)alkenols by using specific chiral ligands and hypervalent-iodine compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Brandon L. Frey, Phong Thai, Lauv Patel, David C. Powers
Summary: In this study, electrochemical data for 70 aryl iodides were reported. The potential for one-electron oxidation of 4-substituted aryl iodides to iodanyl radicals was found to be well-correlated with standard Hammett parameters. Additional data for 3- and 2-substituted aryl iodides, including structures with potentially chelating 2-substituents commonly encountered in hypervalent iodine reagents, were also presented. Potential decomposition processes relevant to the (in)stability of iodanyl radicals were discussed. It is anticipated that these collected data will advance the design and application of aryl iodide electrocatalysis.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Physical
Marta Papis, Francesca Foschi, Sara Colombo, Egle Maria Beccalli, Camilla Loro, Gianluigi Broggini
Summary: The combination of copper catalysts and hypervalent iodine reagents is a versatile tool in organic synthesis for the functionalization of unactivated substrates, allowing access to various classes of compounds.
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)
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.
Article
Chemistry, Applied
Yuki Umakoshi, Yusuke Takemoto, Akira Tsubouchi, Viktor V. Zhdankin, Akira Yoshimura, Akio Saito
Summary: A transition metal iodine catalyst is used to synthesize oxazoles through C-C bond formation between unfunctionalized alkynes and arenes, resulting in the introduction of aryl groups into the side chain of the compounds.
ADVANCED SYNTHESIS & CATALYSIS
(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)
Article
Chemistry, Multidisciplinary
Yuriy Zatsikha, Briana R. Schrage, Tanner S. Blesener, Laurel A. Harrison, Christopher J. Ziegler, Victor N. Nemykin
Summary: In this study, a sterically strained 32 pi-electron antiaromatic bis-BODIPY macrocycle was prepared and characterized. The fluorescence in this macrocycle was quenched, unlike regular BODIPYs. The NMR spectra of the macrocycle showed broad signals due to the vibronic freedom of the p-divinylbenzene fragments. EPR spectra in solution and in solid state confirmed the closed-shell quinoidal structure of the macrocycle, ruling out its possible diradicaloid nature.
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, Physical
Rachel K. Swedin, Andrew T. Healy, Jacob W. Schaffner, Ilya A. Kuzmin, Yuriy V. Zatsikha, Victor N. Nemykin, David A. Blank
Summary: The excited state dynamics in two fully characterized pyridoneBODIPY-fullerene complexes were investigated. Efficient energy transfer and internal conversion were observed in the presence of the fullerene, allowing the excited state energy to be transferred back to the pyridoneBODIPY chromophore. The attachment chemistry of the fullerene affected the triplet-triplet energy transfer and the relaxation rate of the final triplet state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
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)