Article
Chemistry, Physical
Anthony R. Allen, Jia-Fei Poon, Rory C. McAtee, Nicholas B. Watson, Derek A. Pratt, Corey R. J. Stephenson
Summary: Alkene aminoarylation with arylsulfonylacetamides via visible light-mediated radical Smiles-Truce rearrangement is a convenient method for synthesizing the traditional arylethylamine pharmacophore generated by multistep reactions. Our detailed study on the mechanism suggests that the reaction may proceed through a stepwise process or concerted fashion.
Article
Chemistry, Organic
Zhan-Cai Li, Yu Zhang, Bing-Xia Yan, Xiao-Ning Wang, De-Hua Zhai, Qiang Li, Hong-Xing Zheng, Chang-Qiu Zhao
Summary: Biphenyl derived secondary phosphine oxides with 2'-hydroxyl were synthesized and converted to hydroxymethyl phosphine oxides. Chlorination and cyclization led to the formation of a series of P,O-heterocycles. Under LDA treatment, rearrangement occurred to stereoselectively produce hydroxyl substituted cyclic phosphines. The rearrangement was proposed to involve intra-molecular aromatic substitution reactions, resulting in the conversion of P-stereogenic secondary phosphine oxide to a P,C,axial-stereogenic P-cycle.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Polymer Science
Catherine Marestin, Saber Chatti, Regis Mercier
Summary: Efforts have been made to synthesize phosphonic acid-containing poly(aryl ether)s (PAEs) by synthesizing two bisphenol monomers bearing phosphonic ester groups. The study identified specific experimental conditions to prevent side reactions and successfully prepared high molecular weight PAEs, which were further obtained containing free acid phosphonic groups through controlled hydrolysis.
Article
Polymer Science
Naoki Shida, Kazuyuki Ninomiya, Natsuki Takigawa, Keiichi Imato, Yousuke Ooyama, Ikuyoshi Tomita, Shinsuke Inagi
Summary: A postpolymerization nucleophilic aromatic substitution reaction is used to efficiently diversify conjugated polymers, with complete substitution achieved by thiophenol derivatives and carbazole, while disubstitution occurs with para-selectivity by phenol derivatives.
Article
Chemistry, Applied
Taku Shoji, Yukino Ariga, Naoko Sakata, Daichi Ando, Shigeki Mori, Tetsuo Okujima, Ryuta Sekiguchi, Shunji Ito
Summary: Bronsted acid-mediated intramolecular cyclization of 2-amidoazulene derivatives led to the formation of 2-perfluoroalkylazuleno[2,1-d]pyrimidin-4(3H)-ones. Heating of these products in phosphoryl chloride resulted in 4-chloro-2-perfluoroalkylazuleno[2,1-d]pyrimidines. The reactivity of these pyrimidin-4(3H)-ones and pyrimidine derivatives towards electrophilic and nucleophilic substitution reactions was evaluated, and various functional groups were found to be incorporated into these derivatives. NMR studies, NICS calculations, and single-crystal X-ray structure analyses revealed the structural features including bond-length alternation of the azuleno[2,1-d]pyrimidin-4(3H)-ones and pyrimidine derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Correction
Chemistry, Multidisciplinary
Kun-Xu Teng, Li-Ya Niu, Yan-Fei Kang, Qing-Zheng Yang
Summary: This study discusses a rational design of a dual lock-and-key supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy.
Article
Chemistry, Multidisciplinary
Eduardo Rodrigo, Rainer Wiechert, Magnus W. Walter, Wilfried Braje, Herve Geneste
Summary: By using KOH, the direct F to OH exchange of aromatic and heteroaromatic substrates can be achieved under mechanochemical conditions, making the process more atom economical and environmentally friendly compared to other methods.
Review
Chemistry, Organic
Harry C. Sample, Mathias O. Senge
Summary: The study details the SNAr reactions of seven types of porphyrinoids with different pyrrole units, analyzing the substitution dependent on the type of nucleophile and the site of substitution. Nucleophilic substitution on porphyrinoids is found to be an cost-effective procedure with the ability to yield complex substituent patterns, regardless of the type of porphyrinoid.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Wei Chen, Hui Wang, Nicholas E. S. Tay, Vincent A. Pistritto, Kang-Po Li, Tao Zhang, Zhanhong Wu, David A. Nicewicz, Zibo Li
Summary: PET is a powerful imaging technology used to visualize and measure metabolic processes and obtain unique information about drug candidates. The development of new and improved molecular probes in PET is crucial, but progress is restricted by the lack of efficient and simple labeling methods. This study introduces a method for constructing C-F-18 bonds through direct halide/F-18 conversion in electron-rich halo(hetero)arenes, enabling rapid diversification of PET probes.
Review
Biochemistry & Molecular Biology
Ritesh Gautam, Ian Geniza, Scott T. Iacono, Chadron M. Friesen, Abby R. Jennings
Summary: Perfluoropyridine (PFPy) is a highly reactive organofluorine compound that has versatile applications, including chemical synthesis, fluoropolymers, and fluorinated network materials.
Article
Chemistry, Multidisciplinary
Jie Zhang, Zuowei Xie
Summary: This study reported a pyridine-enabled transition-metal-free regioselective nucleophilic aromatic cage B(4)-H amination reaction, offering a selective amination strategy for o- and m-carboranes. Control experiments indicated the crucial role of magnesium complex, bidentate ligand, and reaction temperature in the process of cage isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Junu Kim, Yusuke Hayashi, Sara Badr, Kazuya Okamoto, Toshikazu Hakogi, Haruo Furukawa, Satoshi Yoshikawa, Hayao Nakanishi, Hirokazu Sugiyama
Summary: Extensive kinetic studies were conducted to identify new reaction pathways and evaluate their feasibility in resolving contradictions in the understanding of amination reaction via nucleophilic aromatic substitution. The use of different bases in the reaction system resulted in distinct concentration profiles, including sigmoidal profiles in both starting material and product. These profiles suggests that a species acting as a catalyst evolves during the reaction, indicating that the reaction mechanism changes depending on the specific base. The study presents novel identification of reaction conditions and additives that induce mechanism changes, while elucidating the catalytic effect of a newly discovered species formed during the reaction, thereby resolving the previously conflicting explanations of the reaction pathways.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Guangyu Zhang, Jiaxi Xu
Summary: In this study, a new cascade reaction involving the nucleophilic substitution, O[1,3] sigmatropic shift, Smiles rearrangement, and amide and ester exchange reaction was observed. It resulted in the synthesis of 2-((2/4-nitroaryl)amino)aryl carboxylate derivatives from 2/4-nitroaryl halides and N-acyl-N-arylhydroxylamines in the presence of sodium hydride in THF. This reaction provides a novel strategy for the synthesis of 2-hydroxydiarylamine derivatives under transition metal-free conditions.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Alexei Lukin, Mikhail Chudinov, Tatiana Vedekhina, Elizaveta Rogacheva, Lyudmila Kraeva, Olga Bakulina, Mikhail Krasavin
Summary: This study reported a new derivative of ciprofloxacin and synthesized 36 new fluoroquinolone derivatives through the synthesis of previously reported and newly synthesized derivatives of 1-oxa-9-azaspiro[5.5]undecane. The antibacterial experiments showed that compared to ciprofloxacin, the new compounds had a narrower activity spectrum, but displayed significant activity against two strains: Acinetobacter baumannii 987 (R) and Bacillus cereus 138 (R).
Article
Biochemistry & Molecular Biology
Kotaro Kikushima, Haruka Koyama, Kazuki Kodama, Toshifumi Dohi
Summary: The study demonstrates metal-free synthesis of monosubstituted aromatic compounds via nucleophilic aromatic substitution reactions, resulting in functionalized PTH derivatives through two-step reactions, some of which show potential application as photocatalysts for carbon-halogen bond reduction.
