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, Organic
Tyll Freese, Lukas J. Patalag, J. Luca Merz, Peter G. Jones, Daniel B. Werz
Summary: This study reports an improved direct access to red-emitting BOIMPY fluorophores, starting from easily available benzimidazole-2-carboxylic acids, which greatly enhances yields and saves costs, facilitating the synthesis of novel unsymmetrical BOIMPY motifs. As a result, the BOIMPY scaffolds derived from the BODIPY core become more accessible for applications as fluorophores at the appealing red edge of the visible spectrum.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Thomas J. Kuczmera, Andreas Boelke, Boris J. Nachtsheim
Summary: This study presents a systematic investigation of ethynyl N-heterocycle-substituted-lambda(3)-iodanes (ENHIs) and evaluates their potential applications in alkyne group transfer reactions through synthesis and reactivity assessment.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Han Huang, Haiyan Zhang, Qiaoling Wang, Youwen Sun, Lei Su, Wenru Xu, Yi Ma, Sheng Kong, Guozhu Zhang, Rui Guo
Summary: We have developed a copper-catalyzed three-component asymmetric radical 1,4-aryl/alkynylation of 1,3-enynes using inexpensive and readily available diaryliodonium salts as precursors. The reaction relies on the use of IPOPA as chiral ligands to generate aryl radicals. This reaction exhibits good compatibility and provides an efficient method for constructing highly enantioselective tetrasubstituted axially chiral allene compounds.
Article
Chemistry, Multidisciplinary
Sanjay Telu, Susovan Jana, Mohammad B. Haskali, Bo Yeun Yang, Jimmy E. Jakobsson, Qunchao Zhao, Karla M. Ramos-Torres, Pedro Brugarolas, Victor W. Pike
Summary: Efficient methods for labeling aryl trifluoromethyl groups using readily accessible aryl(mesityl)iodonium salts have been developed. The labeling can be achieved with either carbon-11 or fluorine-18, resulting in high chemoselectivity and good to excellent radiochemical yields. The method is applicable to a wide range of substrates, including substituted heteroaryl(mesityl)iodonium salts, and has been successfully demonstrated on several drug-like molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Raktim Abha Saikia, Khanindra Talukdar, Debabrat Pathak, Bipul Sarma, Ashim Jyoti Thakur
Summary: Here, a general method for copper-catalyzed N-arylation of isatoic anhydrides with unsymmetrical iodonium salts at room temperature is reported. The protocol is mild and simple, employing aryl(TMP)iodonium trifluoroacetate as the arylating partner, and provides access to N-arylated isatoic anhydrides with diverse aryl groups in moderate to excellent yields (53-92%). The methodology is also compatible with substituted isatoic anhydrides and can be used for the synthesis of biologically relevant fenamic acid derivatives and N,N'-diarylindazol-3-ones in a one-pot step economical system, as demonstrated here. The scale-up synthesis of flufenamic acid is also illustrated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Naoto Sugisawa, Kohei Nakabayashi, Hiroki Sugisawa, Shinichiro Fuse
Summary: We have developed one-step syntheses for unsymmetrical sulfamides and N-substituted sulfamate esters by modifying the nucleophile and tertiary amine. Symmetrical sulfite formation was prevented by changing the tertiary amine during the synthesis of N-substituted sulfamate esters. The impact of tertiary amines was explained using linear regression. Our approach allows for rapid production (<= 90 s) of desired products with labile acidic and/or basic groups under mild (20 degrees C) conditions, eliminating the need for tedious purification.
Letter
Chemistry, Organic
Wenxiu Gao, Dong Zhang, Xiaoyu Zhang, Xinying Cai, Peizhong Xie, Teck-Peng Loh
Summary: A Pd/Ca catalytic system for the unsymmetrical bis-allylation of malononitrile was developed using conjugated dienes and allylic alcohols as allylic reagents. This system shows high chemoselectivity and efficiency, allowing the synthesis of diverse 1,6-dienes.
Review
Chemistry, Organic
Kotaro Kikushima, Elghareeb E. Elboray, J. Oscar C. Jimenez-Halla, Cesar R. Solorio-Alvarado, Toshifumi Dohi
Summary: This review summarizes the double functionalization of carbon-iodine(iii) and ortho carbon-hydrogen bonds using diaryliodonium(iii) salts, which has significant application value in molecular synthesis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Kai N. Sands, Benjamin S. Gelfand, Thomas G. Back
Summary: Aryl selenonic acids were synthesized from aryl bromides via a one-pot method, with yields ranging from 77-90%. The synthesis involved metalation, selenation, oxidation with hydrogen peroxide, and ion exchange. One derivative readily dehydrated to form a cyclic selenonic ester, while two minor byproducts were identified as mixed salts of aryl selenonic acids with either aryl seleninic or selenious acid through X-ray crystallography.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Xinyin Wu, Pan Gao, Feng Chen
Summary: The utilization of aryl radicals as open-shelled intermediates is important in synthetic chemistry, but current methods for generating aryl radicals are inefficient. Sulfonium salts have emerged as appealing sources for generating aryl radicals due to their unique structure and chemical tendencies. This review focuses on the mechanisms of cleaving C-S bonds in sulfonium salts to generate aryl radicals. The development of synthetic applications using aryl sulfonium salts as precursors is also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
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, Organic
Yi-Bing Yin, Xiao-Shui Peng, Henry N. C. Wong
Summary: A one-pot iron-catalyzed cross-coupling protocol was developed for the synthesis of unsymmetrical biaryls using aryl chlorides, aryl bromides, and magnesium metal. The key step in this reaction is the in situ generation of Grignard reagents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Zhenhua Liu, Yang Fang, Yi Liu, Wei Fu, Xingxing Gan, Wen Gao, Bo Tang
Summary: A novel difunctionalization of aryldiazonium salts was developed for the one-step generation of symmetric and asymmetric p-azophenols. This approach utilizes sequential regioselective aromatic C-O and C-N bond construction under mild reaction conditions, providing a new reaction strategy for the synthesis of p-azophenols.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Jen-Chun Hsueh, Fu-En Szu, Yin-Yin Yu, Man-kit Leung
Summary: A one-pot synthesis of 2,4-disubstituted quinazoline derivatives from halofluorobenzenes with nitriles via sequential nucleophilic addition and SNAr reaction was reported. The method is transition metal free, easy to operate, and all the starting materials are commercially available.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
