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
Avery J. To, Graham K. Murphy
Summary: In this study, it was discovered that cyclic diaryliodonium salts can act as effective Lewis-acidic halogen-bond donor catalysts in the Nazarov cyclization reaction.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shubhendu S. Karandikar, Avik Bhattacharjee, Bryan E. Metze, Nicole Javaly, Edward J. Valente, Theresa M. McCormick, David R. Stuart
Summary: Diarylhalonium compounds play important roles as reagents and catalysts in organic synthesis, with the key reactivity of the three center, four electron bond requiring refinement for broader applicability. The combination of Density Functional Theory, Natural Bond Orbital Theory, and X-ray structure data can provide insights into the bonding and structure of these compounds.
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
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
Agricultural Engineering
Xudong Liu, Florent P. Bouxin, Jiajun Fan, Richard Gammons, Vitaliy L. Budarin, Changwei Hu, James H. Clark
Summary: By utilizing Fe(OTf)(3) as a Lewis acid and combining it with microwave heating, efficient delignification and depolymerization of lignin in birch sawdust were achieved, resulting in a high yield of monophenolic compounds.
INDUSTRIAL CROPS AND PRODUCTS
(2021)
Article
Chemistry, Organic
Imran Kazi, Anuradha Nandy, Raji Selvam, Govindasamy Sekar
Summary: An efficient method for transition metal-free halogen bond-assisted regioselective C-H arylation of 2-phenylimidazo-[1,2-a]pyridines under visible-light condition has been developed. The halogen bond between an aryl halide and base (KOBu)-Bu-t initiates an electron transfer process and generates an aryl radical, which catalyzes its coupling with 2-phenylimidazo-[1,2-a]pyridines to give arylated products in good yield. This methodology has been successfully utilized to synthesize antileishmanial agents.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Rory T. Gallagher, Soocheta Jha, Bryan E. Metze, David R. Stuart
Summary: This article describes the development of a C-O coupling reaction between aryl(2,4,6-trimethoxyphenyl)iodonium salts and aliphatic alcohols under weak base conditions. The scope of the reaction and its yield in 16 examples are presented, ranging from moderate to high (54-96%). The article also discusses the limitations of the reaction and reveals a complex network of mechanistic reactions, including the generation of aryne compounds and oxidation of the alcohol nucleophile.
Article
Chemistry, Organic
Regina M. Oechsner, Ivo H. Lindenmaier, Ivana Fleischer
Summary: We present a nickel catalyzed C-S cross-coupling reaction of aryl and alkenyl triflates with alkyl thiols. By using an air-stable nickel precatalyst, various thioethers could be synthesized under mild reaction conditions within a short reaction time. The reaction demonstrated a broad substrate scope, including pharmaceutically relevant compounds.
Article
Chemistry, Multidisciplinary
Zhiyuan Bao, Chao Chen
Summary: An efficient method for the synthesis of multi-substituted cyclic imides was developed using cyanoesters and diaryliodonium salts. This method involves a cascade of N-arylation-acylation and rearrangement reactions, producing the desired heterocycles in high yields. The method has a broad substrate scope, excellent functional group compatibility, and can be extended to fused cyclic imides.
CHINESE CHEMICAL LETTERS
(2023)
Review
Chemistry, Medicinal
Thierry Besson, Corinne Fruit
Summary: This review highlights recent synthetic advances in the late-stage C(sp2)-N and C(sp2)-C(sp2) bond-forming reactions under metal-free conditions using diaryliodonium salts as arylating reagents, and discusses their applications in the synthesis of new arylated bioactive heterocyclic compounds.
Review
Chemistry, Organic
Dan Wang, Qian Li, Mengting Li, Zhengyin Du, Ying Fu
Summary: Hypervalent iodine compounds, in particular diaryliodonium salts, have been widely used in organic synthesis due to their low toxicity, mild conditions, and high selectivity. These compounds serve as efficient alternatives to heavy metal-based oxidants and expensive organometallic catalysts, showing good reactivity and selectivity in various transformations.
CURRENT ORGANIC CHEMISTRY
(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)
Review
Chemistry, Multidisciplinary
Jiarong Shi, Lianggui Li, Yang Li
Summary: Arynes are highly active organic intermediates used in the rapid synthesis of substituted arenes, with o-silylaryl triflates being the most frequently employed precursors. The resurgence in aryne chemistry over the past 20 years is largely attributed to the widespread use of Kobayashi's method, which involves fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group. This review provides an overview of the history, achievements, and applications of Kobayashi's method in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.
Article
Chemistry, Multidisciplinary
Xinyu Chen, Na Yang, Wen Zeng, Lei Wang, Pinhua Li, Hongji Li
Summary: A mild dearomative [5+2]/[2+2] cycloaddition of 1H-indoles with ortho-(trimethylsilyl)aryl triflates was reported, leading to the synthesis of dibenzo[b,e]azepine derivatives in moderate to good yields. Increasing steric hindrance at the C2-position of 1H-indoles directs the reaction towards a [2+2] cycloaddition pathway. Mechanistic investigations suggest that the reaction proceeds through a [2+2] cycloaddition followed by a ring expansion to form the [5+2] cycloaddition product.
CHEMICAL COMMUNICATIONS
(2021)
