Article
Chemistry, Organic
Julien Borrel, Jerome Waser
Summary: In this study, a simplified synthesis method for generating Ethynylbenziodoxolones (EBXs) in one pot and directly applying them to substrate functionalization was reported. By bypassing the mandatory isolation and purification steps, this approach led to a more efficient synthesis and successful application in various transformations to obtain a diverse range of alkynylated products.
Article
Chemistry, Multidisciplinary
Loic Habert, Kevin Cariou
Summary: In this study, the aerobic iodoarene catalysis was achieved by using a pyrylium photocatalyst under blue light irradiation, allowing for the use of low catalytic loading of both catalysts under very mild operating conditions. This unprecedented dual organocatalytic system provides a powerful and efficient methodology for spiro-cyclization of amides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Flemming Heinen, Dominik L. Reinhard, Elric Engelage, Stefan M. Huber
Summary: This study presents the first application of a bidentate bis(iodolium) salt as an organocatalyst in various reactions, surpassing the performance of iodine(I)-based organocatalysts and approaching that of strong Lewis acids like BF3. Coordination of the bidentate XB donor to the substrate was confirmed through structural analysis and DFT calculations of the transition states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Akira Yoshimura, Christopher D. Huss, Mackenzie Liebl, Gregory T. Rohde, Scott M. Larson, Gunnar B. Frahm, Mattew W. Luedtke, Tanner J. Schumacher, Zachary S. Gardner, Viktor V. Zhdankin, Pavel S. Postnikov, Mekhman S. Yusubov, Tsugio Kitamura, Akio Saito
Summary: Pseudocyclic beta-trifluorosulfonyloxy vinylbenziodoxolones were prepared and their structures were established by single crystal X-ray diffraction. The reaction of these compounds with azide anion led to beta-azido vinylbenziodoxolones, demonstrating vinylic nucleophilic substitution.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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, 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, Multidisciplinary
Andreas Boelke, Thomas J. Kuczmera, Enno Lork, Boris J. Nachtsheim
Summary: The article explores the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts, particularly as potent XB-donors in halogen-bond catalysis. Among the variety of NHISs tested, N-methylated dicationic NHISs exhibited the highest reactivity in all investigated catalytic applications, surpassing previously described monodentate XB-donors based on iodine(I) and (III) as well as the strong Lewis acid BF3.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Pierre Palamini, Julien Borrel, Mael Djaid, Morgane Delattre, Jerome Waser
Summary: We report the synthesis of ketene dithioarylacetals in 40-97% yield using thiophenols and acyl-EBXs generated in situ from a common hypervalent iodine precursor and alkynyl trifluoroborate salts. The products could be further modified to afford functionalized ketene dithioacetals and various S-substituted heterocycles.
Review
Chemistry, Organic
Fumito Saito
Summary: This article reviews the significant advances in sulfenate protocols, including alkylation and arylation, and provides future directions for research in this field.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Lotte Stockhammer, Johannes Schoergenhumer, Christopher Mairhofer, Mario Waser
Summary: This study introduces an unprecedented strategy for the asymmetric alpha-chlorination of beta-keto esters using simple Cinchona alkaloid catalysts and hypervalent iodine-based Cl-transfer reagents. The Cinchona species was found to act as a nucleophilic catalyst, generating a chiral electrophilic Cl-transfer reagent in situ, leading to good yields and enantioselectivities under operationally simple conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, Organic
Jianji Li, Bo Liu, Yifan Hu, Xianwei Li, Yanping Huo, Qian Chen
Summary: A hypervalent iodine-induced disulfenylation of thiophene derivatives with thiophenols via a thiyl radical reaction pathway has been achieved. This transformation provides direct synthetic access to 2,3-disulfenylated thiophene derivatives in 34-78% yields with good functional group compatibility under mild reaction conditions.
TETRAHEDRON LETTERS
(2022)
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, 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)
Article
Chemistry, Applied
Vojtech Docekal, Tereza Koberova, Jan Hrabovsky, Andrea Vopalenska, Robert Gyepes, Ivana Cisarova, Ramon Rios, Jan Vesely
Summary: A new asymmetric organocatalytic cascade reaction was reported for the synthesis of enantiopure chiral boron dipyrromethenes (BODIPYs), with high isolated yields and enantiomeric excesses. The method showed synthetic versatility and was successfully applied to a series of additional transformations of the corresponding optically pure compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Michal Urban, Martin Nigrini, Ivana Cisarova, Jan Vesely
Summary: The atom-economic method developed using a chiral amine-squaramide Mannich reaction and Au(I)-catalyzed hydroamination can efficiently prepare novel bispirocyclic compounds containing three fused heterocyclic scaffolds. This synthetic strategy, whether performed stepwise or as a one-pot process, enables the formation of chiral bispirocyclic [oxindole-pyrrolidine-pyrazolones] with high yields (up to 75%) and excellent enantioselectivities (up to 99%).
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Viraj A. Bhosale, Martin Nigrini, Martin Dracinsky, Ivana Cisarova, Jan Vesely
Summary: The study presents a versatile method for the synthesis of chiral 2H-1,4-benzoxazines using chiral phosphoric acid catalysis, achieving high yields and enantioselectivity under mild conditions. This strategy expands on traditional methods and provides access to key intermediates for therapeutic candidates, such as prostaglandin D2 receptor antagonists and MI positive allosteric modulator (PAM) compound VU0486846.
Article
Chemistry, Multidisciplinary
Klara Kohoutova, Vojtech Docekal, Michael J. Ausserlechner, Nora Kaiser, Andrej Tekel, Raju Mandal, Matej Horvath, Veronika Obsilova, Jan Vesely, Judith Hagenbuchner, Tomas Obsil
Summary: Increased FOXO3 nuclear localization is involved in neuroblastoma chemoresistance and tumor angiogenesis. Inhibition of FOXO3 is a promising strategy for enhancing antitumor immune responses and suppressing therapy resistance in cancer cells. (4-propoxy)phenylpyrimidinylguanidine has been identified as a FOXO3 inhibitor in cancer cells. The synthesis and structure-activity relationship study of its derivatives showed that some compounds are more potent than the parent compound in inhibiting FOXO3-induced gene transcription. These findings may contribute to the development of therapeutics for inhibiting FOX transcription factors.
Article
Chemistry, Multidisciplinary
Martin Kamlar, Michal Urban, Jan Vesely
Summary: Over the past decade, the combination of organocatalysis and transition metal catalysis has become an important tool for synthesizing optically pure compounds with chiral quaternary centers, including spiro heterocyclic molecules. The dominant methods in enantioselective synthesis of spiro heterocyclic compounds involve chiral aminocatalysis, NHC catalysis, as well as non-covalent catalysis using chiral phosphoric acids, thiourea, and squaramide derivatives. This review article provides a summary of enantioselective methods for constructing spirocyclic heterocycles using a combination of organocatalysis and transition metal catalysis.
Article
Chemistry, Organic
Andrea Vopalenska, Vojtech Docekal, Simona Petrzelova, Ivana Cisarova, Jan Vesely
Summary: The present study reports an asymmetric organocascade reaction that efficiently catalyzes the reaction between oxindole-derived alkenes and 3-bromo-1-nitropropane using a bifunctional catalyst. The reaction produces spirooxindole-fused cyclopentanes in moderate-to-good isolated yields (15-69%) with excellent stereochemical outcomes. The synthetic utility of the protocol is demonstrated through additional transformations of the resulting spirooxindole compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Anastasia Kurbanova, Martin Nigrini, Kinga Golabek, Ondrej Vesely, Jan Vesely
Summary: Synthetic organic chemistry often requires multiple steps and expensive catalysts for the synthesis of functionalised tetrahydropyrans. In this study, we tested zeolites as eco-friendly and industrially relevant catalysts for the synthesis of 2-phenyltetrahydropyran. The results showed that zeolites favor the formation of the desired product, and the reaction kinetics depend on the number of acid sites, rather than the textural properties.
MICROPOROUS AND MESOPOROUS MATERIALS
(2023)
Article
Chemistry, Organic
Ladislav Loska, Vojtech Docekal, Ivana Cisarova, Jan Vesely
Summary: The study presents an asymmetric NHC-catalyzed formal [4 + 2] cycloaddition of heterocyclic alkenes with an azolium-dienolate intermediate. The reaction is achieved without external oxidation of the Breslow intermediate. Good yields (typically about 90%) and stereochemical outcomes (in most cases, dr > 20/1, and ee = 70-99%) were obtained for heterocyclic cyclohexenones. The synthetic utility of the protocol was demonstrated by the scope of heterocyclic alkenes.
Article
Chemistry, Organic
Martin Kamlar, Ivana Cisarova, Jan Vesely
Summary: A Bronsted acid-catalyzed synthesis of tetrasubstituted allenyl compounds decorated with heterocyclic sulfenyl group is reported in this study. The reaction can readily proceed from available propargylic alcohols in the presence of pentacarboxycyclopenatadienes (PCCPs) as organocatalysts. This developed strategy provides tetrasubstituted allene derivatives in high yields and under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Martin Nigrini, Viraj A. Bhosale, Ivana Cisarova, Jan Vesely
Summary: In this study, a highly enantioselective desymmetrization of 3-substituted oxetanes was achieved using a confined chiral phosphoric acid as the catalyst. This metal-free process allows for the efficient synthesis of chiral seven-membered 1,4-benzoxazepines with a high degree of enantiocontrol under mild reaction conditions. The developed synthetic strategy demonstrates its synthetic utility in various enantioselective product transformations, proving its effectiveness in diverse scenarios.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Michael Franc, Ivana Cisarova, Jan Vesely
Summary: The present study investigates an enantioselective cyclization of enals with imidazolone derivatives catalyzed by a combination of achiral Pd(0) complex and chiral secondary amine. Corresponding spirocyclic imidazolones were produced in high yields with moderate diastereoselectivity and excellent enantioselectivity. The developed co-operative catalytic methodology provides a highly substituted spirocyclic scaffold with four stereogenic centers under mild conditions.
Article
Chemistry, Multidisciplinary
Viraj A. Bhosale, Ivana Cisarova, Martin Kamlar, Jan Vesely
Summary: This study presents a novel chiral phosphoric acid (CPA)-catalyzed reaction, allowing for the asymmetric addition of alpha-fluoro(phenylsulfonyl)methane (FSM) derivatives to in situ generated cyclic N-acyliminium. The process demonstrates high stereoselectivity, leading to the formation of biorelevant isoindolinones containing sulfone and fluorine substituents with excellent stereoselectivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
