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, Organic
Shun-Dong He, Xiao-Qiang Guo, Jun Li, Yu-Cheng Zhang, Lian-Mei Chen, Tai-Ran Kang
Summary: In this study, an efficient method for the construction of (Z)-2-iodovinyl aryl ethers and diaryl ethers was developed under metal-, photocatalyst- and light-free conditions in a one-step reaction. The desired products were generated through an S(NAr)2 reaction between phenol and vinyl aryl iodonium salts, resulting in the cleavage of the phenyl-I bond and the formation of the phenyl-O bond. Trisubstituted alkenes and functionalized diaryl ethers could be obtained from these two products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Aleksandra Nilova, Paul A. Sibbald, Edward J. Valente, Gisela A. Gonzalez-Montiel, H. Camille Richardson, Kevin S. Brown, Paul Ha-Yeon Cheong, David R. Stuart
Summary: This study describes a method for synthesizing 1,2,3,4-tetrasubstituted benzenoid rings, addressing previous challenges in regioselective synthesis of these compounds. By using substituted arynes derived from aryl(Mes)iodonium salts, a range of densely functionalized 1,2,3,4-tetrasubstituted benzenoid rings can be accessed. The study demonstrates improved conditions for generating arynes at room temperature and in shorter reaction times, allowing for post-synthetic elaboration via palladium-catalyzed coupling.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Matteo Lanzi, Quentin Dherbassy, Joanna Wencel-Delord
Summary: A general, safe, and high-yielding strategy to access cyclic diaryl lambda(3)-bromanes is reported in this study, featuring reactivity complementary to that of lambda(3)-iodanes to generate arynes under mild reaction conditions in the presence of a weak base. Mechanistic studies unambiguously support the aryne generation mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Matteo Lanzi, Torben Rogge, Tan Sang Truong, K. N. Houk, Joanna Wencel-Delord
Summary: Hypervalent chloranes are rare and poorly explored reagents that possess unique electronic properties. This study reports highly chemo- and regioselective, metal-free, and mild C-C and C-O couplings using these chloranes. Mechanistic studies reveal the unprecedented reactivities and selectivities of these systems and the involvement of aryne intermediates. The synthetic potential of these transformations is demonstrated through post-functionalization of the coupling products obtained from chloranes and phenols under different conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Applied
Akira Yoshimura, Akio Saito, Viktor V. Zhdankin
Summary: Hypervalent iodine compounds, particularly those based on the benziodoxole heterocyclic system, are widely used as reagents and catalysts in modern organic chemistry. These cyclic hypervalent iodine reagents exhibit higher stability compared to their acyclic analogues, allowing for the safe handling and preparation of reagents with special ligands such as azido, cyano, and trifluoromethyl groups. They have been utilized for the transfer of substituents on hypervalent iodine to organic substrates under various reaction conditions. This review focuses on the recent synthetic applications of cyclic hypervalent iodine(III) reagents with different ligands, including N-3, NHR, CN, CF3, SCF3, OR, OAc, ONO2, and C(=N-2)CO2R, mainly in the past 5 years.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Mattis Damrath, Lucien D. Caspers, Daniel Duvinage, Boris J. Nachtsheim
Summary: Two simple methods for synthesizing O- and N-bridged diaryliodonium triflates are described. Different derivatizations were applied to demonstrate their usefulness as building blocks and to gain a deeper understanding of their general reactivity.
Article
Chemistry, Applied
Andres Vazquez-Lopez, James E. Allen, Sarah E. Wengryniuk
Summary: A metal-free olefin diamination via a heterocyclic group transfer (HGT) reaction of I(III) N-HVI reagents has been reported, resulting in the synthesis of 3-aminopiperidines with high selectivity. The HGT strategy utilizes heteroarenes as oxidatively masked amine nucleophiles to produce (hetero)arylonium salt products, which can be easily isolated and further diversified. Mechanistic studies suggest that the 6-endo selectivity is attributed to the ring opening of an intermediate aziridinium ion.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Pragya Sharma, Neha Taneja, Sanjay Singh, Chinmoy K. Hazra
Summary: A three-component, solvent-dependent, Bronsted-acid-catalyzed reaction has been developed for the synthesis of potential drug candidate 3-aryl-1-indanones. This reaction features high regioselectivity, broad substrate generality, easy scalability, and diverse starting materials. Detailed mechanistic insight leads to a feasible reaction pathway.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yulia A. Vlasenko, Thomas J. Kuczmera, Nikita S. Antonkin, Rashid R. Valiev, Pavel S. Postnikov, Boris J. Nachtsheim
Summary: Here, the application of azole-stabilized diaryliodonium salts with additional thiophene-2-yl-ligands as metal-free nucleophilic arylation substrates is presented. In addition to their synthesis, their use in chemoselective nitrations, oxygenations, aminations, and thiolations under umpolung conditions is demonstrated. Convenient one-pot procedures based on their in situ formation are also discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Lei Zhang, Wangzhen Bao, Yuchen Liang, Wenjing Pan, Dongyang Li, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: This study demonstrates the reversal of stereoselectivity in MBH-type [3,3]-rearrangement by using a new pair of rearrangement partners, leading to the synthesis of different types of alpha-aryl alpha,beta-unsaturated carbonyl derivatives. Mechanistic studies provide insights into the reaction pathway and the opposite stereoselectivities observed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xu Liu, Limin Wang, Hao-Yang Wang, Jianwei Han
Summary: In this study, an efficient site-selective O-arylation method for complex arenes involving intramolecular aryl rearrangement is presented. The reaction is facilitated by diaryliodonium salts bearing vicinal trifluoromethanesulfonate (OTf) groups. The procedure starts with selective C-H bond activation of arenes, followed by nucleophilic aromatic substitution (SNAr) to convert them into diaryl ethers. This synthetic method successfully provides complex diaryl ether derivatives, demonstrating its practicality in the diversification of functionalized arenes and pharmaceutical agents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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
Serena Monticelli, Wolfgang Holzer, Thierry Langer, Alexander Roller, Berit Olofsson, Vittorio Pace
Article
Chemistry, Multidisciplinary
Laura Castoldi, Ester Maria Di Tommaso, Marcus Reitti, Barbara Grafen, Berit Olofsson
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Gabriella Kervefors, Leonard Kersting, Berit Olofsson
Summary: A transition metal-free approach using unsymmetric diaryliodonium salts with anisyl ligands has been developed for the N-arylation of amino acid derivatives, achieving high chemoselectivity and yields. This method is applicable for transferring electron deficient, electron rich, and sterically hindered aryl groups, and a cyclic diaryliodonium salt was successfully employed. The N-arylated products were obtained with retained enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Gabriella Kervefors, Kumar Bhaskar Pal, Gergely L. Tolnai, Mukul Mahanti, Hakon Leffler, Ulf J. Nilsson, Berit Olofsson
Summary: The study focused on synthesizing a series of O3-arylated galactosides and their inhibitory effects on galectin-3, leading to the discovery of a compound with promising affinity and selectivity for both the N- and C-terminal domains of galectin-9.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Erika Linde, David Bulfield, Gabriella Kervefors, Nibadita Purkait, Berit Olofsson
Summary: This study combines nucleophilic aromatic substitution and hypervalent iodine-mediated arylations to achieve a transition-metal-free difunctionalization of N and O-nucleophiles, providing di-and triarylamines and diaryl ethers in one single step. The unique reactivity discovered with specifically designed fluorinated diaryliodonium salts unveils novel reaction pathways in hypervalent iodine chemistry. The methodology tolerates a wide variety of functional and protecting groups, allowing for easy derivatization of the products.
Article
Chemistry, Multidisciplinary
Ester M. Di Tommaso, Per-Ola Norrby, Berit Olofsson
Summary: Vinylbenziodoxolones have been identified as efficient reagents for electrophilic vinylations under metal-free conditions. This paper presents the first mechanistic investigation of VBX vinylations, providing insights into the regio- and stereochemical outcome. The findings can be applied to predict the regioselectivity in vinylations of other nucleophile classes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Erika Linde, Niels Knippenberg, Berit Olofsson
Summary: Two regioselective and high-yielding methods for the synthesis of oxygen-bridged cyclic and ortho-aryloxy-substituted acyclic diaryliodonium salts were presented. These novel compounds exhibited complimentary reactivities in chemoselective arylation reactions, delivering a range of novel ortho-functionalized diaryl ether derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Shobhan Mondal, Ester Maria Di Tommaso, Berit Olofsson
Summary: Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S-diarylation, enabling the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl(vinyl) sulfides. A one-pot strategy combining transition-metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Erika Linde, Shobhan Mondal, Berit Olofsson
Summary: Our group has developed new methods for the synthesis of diaryliodonium salts, which are versatile reagents in organic synthesis and materials chemistry. We have identified limitations in the existing protocols for synthesizing different types of diaryliodonium salts. In this update, we discuss the challenges related to the stability and reactivity of the reagents and propose strategies to overcome these limitations.
ADVANCED SYNTHESIS & CATALYSIS
(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)
Editorial Material
Chemistry, Multidisciplinary
Shobhan Mondal, Berit Olofsson
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Erika Linde, Berit Olofsson
Summary: The diarylation and skeletal diversification of unstrained cyclic amines was explored to expand and modify their properties. A novel class of amino-substituted diaryliodonium salts was synthesized from cyclic amines and converted to highly functionalized diarylamines through a one-pot N-arylation/ring opening reaction. This strategy proved efficient in the late-stage functionalization of natural products and pharmaceuticals, and provided a wide variety of complex diarylamines. The method involves the introduction of two different aryl groups and the retention of an iodo-substituent, allowing for downfield diversification of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ester Maria Di Tommaso, Melanie Walther, Anne Staubitz, Berit Olofsson
Summary: This study developed a synthetic route to access ortho-substituted azobenzenes via novel ortho-substituted azobenzene-functionalized diaryliodonium salts. The selective transfer of the azobenzene moiety to various nucleophiles enables the synthesis of a wide range of ortho-substituted azobenzenes. The photoswitching properties and crystal structure of the reagents were investigated.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemical Research Methods
Erika Linde, Berit Olofsson
Summary: An efficient protocol for the diarylation of aliphatic amines and water with two structurally different aryl groups in one single step was presented, yielding highly functionalized products.
Article
Chemistry, Multidisciplinary
Laura Castoldi, Adam A. Rajkiewicz, Berit Olofsson
CHEMICAL COMMUNICATIONS
(2020)