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
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
Fabienne Hoffmann-Emery, Katrin Niedermann, Pankaj D. Rege, Manuel Konrath, Christian Lautz, Anne Katrin Kraft, Carine Steiner, Fritz Bliss, Andre Hell, Rolf Fischer, Diane E. Carrera, Danial Beaudry, Remy Angelaud, Sushant Malhotra, Francis Gosselin
Summary: A sustainable second-generation process for GDC-0134 was developed to meet the safety and greenness requirements of supplying pivotal clinical studies. The process involved the discovery of alternative solvents and improved reaction conditions, resulting in a significant reduction in process mass intensity and the successful production of a large amount of GDC-0134.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Applied
Nai-Chen Hsueh, Kuan-Ting Chen, Meng-Yang Chang
Summary: A high-yielding one-pot synthesis method for the bis-sulfonyl dibenzooxabicyclo[5.5.0]dodecanes has been developed under open-vessel atmosphere conditions. This method involves a double substitution reaction between 1,3-dichloroacetone and arenesulfinic acid sodium salts, followed by C- and O-alkylation of the resulting 1,3-bis-sulfonylacetones with o-bis(bromomethyl)arenes. The formation of three carbon-carbon single bonds, two carbon-sulfur single bonds, and one carbon-oxygen single bond contributes to the success of this protocol.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Biochemistry & Molecular Biology
Luis R. Domingo, Maria Jose Aurell, Mar Rios-Gutierrez
Summary: The reaction between N-phenyl iminoborane and benzaldehyde, presented by Liu et al., was investigated using Molecular Electron Density Theory (MEDT). The formation of a fused aromatic compound involves three consecutive reactions: the formation of a weak molecular complex between the reactants, an intramolecular electrophilic attack of the activated carbonyl carbon, and a formal 1,3-hydrogen shift. This domino reaction shows similarities to the Bronsted acid catalyzed Povarov reaction.
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.
Article
Chemistry, Multidisciplinary
Yunzhi Lin, Hang Shi
Summary: Aromatic organosilicon compounds are valuable synthetic materials due to their diverse reactivities and compatibility with various functional groups. However, (trialkylsilyl)arenes are considered unsuitable substrates for transition-metal-catalyzed cross-coupling reactions due to low polarity and steric hindrance. This study presents a rhodium-catalyzed addition method for (trialkylsilyl)arenes and electrophiles, and reveals an unexpected stepwise pathway for fluoride-induced desilylation through computational studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
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)
Review
Polymer Science
Silvestre Bongiovanni Abel, Evelina Frontera, Diego Acevedo, Cesar A. Barbero
Summary: This study summarizes the use of organic chemical reactions to functionalize preformed conducting polymers (CPs), focusing on polyaniline (PANI), polypyrrole (PPy), and polythiophene (PT), as well as limited work on other CPs. Two approaches have been taken for the functionalization: direct reactions on the CP chains and reaction with substituted CPs bearing reactive groups. Electrophilic aromatic substitution and nucleophilic conjugate addition are the main reaction mechanisms involved. The improved properties achieved by functionalization of different polymers are also discussed.
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
Shinichiro Fuse, Sena Kanda, Hisashi Masui
Summary: Valuable indole derivatives were synthesized via the sequential 1,2-addition/nucleophilic substitution of indolyl-3-carbaldehydes. Microflow technology was used to suppress undesired reactions caused by unstable intermediates, leading to higher yields and reproducibility. The study provides a rapid and efficient method for the synthesis of structurally diverse indole derivatives.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Huseyin Cem Kiliclar, Cagatay Altinkok, Gorkem Yilmaz, Yusuf Yagci
Summary: A novel visible light induced step-growth polymerization for forming poly(phenylene methylene) was developed, with the effect of different nucleophilic aromatic molecules on the polymerization investigated. The combination of step-growth polymerization with conventional free radical and free radical promoted cationic polymerizations through photoinduced chain-end activation was successfully demonstrated, resulting in highly fluorescent fibers of block copolymers. This versatile photoinduced step-growth polymerization process opens up a new pathway for a new generation of polycondensates and their combination with chain polymers that cannot be obtained by conventional methods.
CHEMICAL COMMUNICATIONS
(2021)
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)
