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, 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, Physical
Hongyang Tang, Simon Smolders, Yun Li, Dirk De Vos, Jannick Vercammen
Summary: In this study, a high regioselective and metal- and oxidant-free method for synthesizing diaryl ethers at room temperature was reported through electrochemical C(sp(2))-H/O-H cross-dehydrogenative coupling of phenols and tertiary anilines. The coupling product was obtained in moderate to excellent yield (up to 83%) with a wide substrate scope and high regioselectivity (>99% for para-substitution).
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
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, 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, Multidisciplinary
Raphael Robidas, Dominik L. Reinhard, Claude Y. Legault, Stefan M. Huber
Summary: Halogen bonding, a non-covalent interaction between Lewis bases and electron-deficient halogen substituents, has garnered increasing attention. Research has focused on designing and evaluating halogen-containing species as donors, with particular interest in organoiodine compounds at the iodine(III) state. These compounds offer unique binding modes due to their electronic and structural properties, leading to their development and evaluation as catalysts in various model reactions.
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.
Article
Chemistry, Organic
Mohamed Elsherbini, Wesley J. Moran
Summary: Cyclic and acyclic diaryliodonium salts were synthesized efficiently without the need for chemical oxidants or generation of chemical waste, with yields ranging from very good to excellent. When scaled-up to 10 mmol, over four grams of product with purity above 95% were obtained in less than three hours, and the solvent mixture could be recycled multiple times with minimal reduction in yield.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Feroze Hussain, Tariq Ahmad Dar, Qazi Naveed Ahmed
Summary: In this study, we present the first mild and one-step direct synthesis of mixed phosphorothioates through the selective generation of O-P(O)-S bonds at room temperature without the need for additives. Additionally, we demonstrate an alternative dimerization strategy using reactions between different model natural products and 1,1-dichloro-N,N-diisopropylphosphanamine. The methodology was also successfully extended to the synthesis of mixed phosphoroselenoates and mixed phosphorothioates bearing two different alcohols.
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.
Article
Chemistry, Applied
Yuna Nishiguchi, Katsuhiko Moriyama
Summary: A new synthetic method was developed with the use of aniline-type hypervalent iodine(III) for direct cyclizations, resulting in high yields of the corresponding products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Artem V. Semenov, Sergey V. Baykov, Natalia S. Soldatova, Kirill K. Geyl, Daniil M. Ivanov, Antonio Frontera, Vadim P. Boyarskiy, Pavel S. Postnikov, Vadim Yu. Kukushkin
Summary: Five new copper(I) complexes were generated and isolated as a solid via a three-component reaction. These complexes consist of dibenzohalolium cation and 1,2,4-oxadiazolate anion, with simultaneous linkage between the O,O atoms of the anion and the halogen atom. The strong three-center halogen bonding between the oxadiazolate moieties and the dibenzohalolium cation was identified as the main force in stabilizing the copper(I) complexes.
INORGANIC CHEMISTRY
(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)
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, Applied
Dmitry I. Bugaenko, Alexander V. Karchava
Summary: Arylation of various phosphines with aryl(mesityl)iodonium triflates under blue light irradiation, followed by oxidative P-N bond cleavage in the in situ generated amino phosphonium salts under hydrolytic conditions, allows for the synthesis of substituted arylphosphine oxides, arylphosphinic, and arylphosphonic amides. This method utilizes visible light as the sole promoter for C-P bond formation, is compatible with a wide range of functional groups, and can be applied for late-stage C-H functionalization of drug molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Debaki Ghosh, Souradeep Basu, Monisha Singha, Joyee Das, Prabuddha Bhattacharya, Amit Basak
TETRAHEDRON LETTERS
(2017)
Article
Chemistry, Organic
Souradeep Basu, Alexander H. Sandtorv, David R. Stuart
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2018)
