Article
Biochemistry & Molecular Biology
Marian Mikolajczyk, Marek Cypryk, Bartlomiej Gostynski, Jakub Kowalczewski
Summary: The mechanisms of three selected identity substitution reactions at phosphorus and sulfur have been investigated using density functional theory (DFT). The results show that these reactions can occur via stepwise or synchronous mechanisms, and DFT method is useful in distinguishing between these mechanisms.
Article
Chemistry, Multidisciplinary
Oluwakemi A. Oloba-Whenu, Chukwuemeka Isanbor
Summary: This study investigated the reaction mechanism and thermodynamic properties of nucleophilic aromatic substitution reactions of different functionalized dinitrobenzenes and corresponding phenoxy derivatives with aniline under different conditions using computational methods. The formation of Meisenheimer complex intermediates was observed, and their stability depended on the number and position of electron-withdrawing groups on the ring. The overall reactions were exothermic and exergonic. From kinetics calculations, it was found that the initial attack of aniline on dinitrobenzene was the rate-limiting step in acetonitrile, while the decomposition of the intermediate MC was the rate-limiting step in vacuum and toluene. The results suggest the prevalence of a multistep SNAr mechanism and indicate that electron-withdrawing groups can enhance the reaction rate.
Article
Biochemistry & Molecular Biology
Sebastian A. Cuesta, F. Javier Torres, Luis Rincon, Jose Luis Paz, Edgar A. Marquez, Jose R. Mora
Summary: In this study, the degradation mechanism of chloroacetanilide herbicides in the presence of four different nucleophiles was theoretically evaluated. The results showed that nucleophiles where a sulfur atom performs the nucleophilic attack are the most effective, and the R groups of the compounds have a negligible effect on the reaction process. Geometrical changes and electronic rearrangements were found to contribute significantly to the activation energy of the process.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Zhensheng You, Kosuke Higashida, Tomohiro Iwai, Masaya Sawamura
Summary: In this study, non-activated aryl fluorides were found to react with potassium diorganophosphinites through nucleophilic aromatic substitution to form tertiary phosphine oxides, with a mechanism involving nucleophile-dependent SNAr reaction pathways.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Chemical
Xinyuan Wu, Qilei Liu, Yujing Zhao, Lei Zhang, Jian Du
Summary: This study presents a new reaction solvent screening framework, establishing a reaction kinetic model based on frontier molecular orbital theory and using an implicit solvation model to quantify the solvent effects on reaction systems independent of transition states. By this method, high-throughput screening of reaction solvents is achieved, and the feasibility and effectiveness of the framework are demonstrated in two case studies.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
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, Multidisciplinary
Panagiota Kafourou, Byoungwook Park, Joel Luke, Luxi Tan, Julianna Panidi, Florian Glocklhofer, Jehan Kim, Thomas D. Anthopoulos, Ji-Seon Kim, Kwanghee Lee, Sooncheol Kwon, Martin Heeney
Summary: This report introduces a new high electron affinity acceptor end group TCNBT for use in n-type organic semiconductors, demonstrating improved molecular properties and orientation. Organic field-effect transistors based on TCNBT showed a high charge-carrier mobility and excellent ambient stability, highlighting the benefits of the cyanated end group and synthetic approach.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Physical
Cheng Yang, Maoshuai Li, Weikang Dai, Jie Wei, Qi Yang, Yi Feng, Wanxin Yang, Jie Ding, Ying Zheng, Mei-Yan Wang, Xinbin Ma
Summary: The nature of the solvent has a significant impact on the activity and selectivity of the hydroformylation reaction. Solvents with stronger electron-donating ability lower the energy barrier for the reaction and promote the formation of glycolaldehyde. Polar aprotic solvents can participate in the reaction through proton transfer, leading to the formation of hydroxymethyl species.
MOLECULAR CATALYSIS
(2022)
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, Organic
Karlis-Eriks Krikis, Irina Novosjolova, Anatoly Mishnev, Maris Turks
Summary: A new method utilizing 1,2,3-triazoles as leaving groups in SNAr-Arbuzov reactions to transform C-N bonds into C-P bonds was developed. C6-phosphonated 2-triazolylpurine derivatives were synthesized for the first time with yields reaching up to 82% in the C-P-bond-forming event. The regioselectivity pattern of C6-position being more reactive towards substitution in the SNAr-Arbuzov reaction of 2,6-bistriazolylpurines was conclusively proven through X-ray analysis.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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
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, Organic
Clayton P. Donald, Amy Boylan, Truong N. Nguyen, Po-An Chen, Jeremy A. May
Summary: The (IPr)GaCl3/AgSbF6, AgSbF6, and GaCl3 catalysts were found to efficiently catalyze the substitution of the hydroxyl group of secondary and tertiary propargylic alcohols with organoboronic acids via C-C bond formation, and GaCl3 catalyst effectively synthesized all-carbon quaternary propargylic centers. These catalysts demonstrated the ability to perform substitutions at carbons bearing alkyl substituents, a capability that was lacking in other systems. The study showed that highly hindered carbon stereocenters, including quaternary centers bearing doubly ortho-substituted aryl rings, could be accessed efficiently using this method.
Article
Chemistry, Multidisciplinary
Jayant Sindhu, Harjinder Singh, J. M. Khurana, Chetan Sharma, K. R. Aneja
CHINESE CHEMICAL LETTERS
(2015)
Article
Optics
Harjinder Singh, Jayant Sindhu, Jitender M. Khurana
JOURNAL OF LUMINESCENCE
(2015)
Article
Chemistry, Multidisciplinary
Harjinder Singh, Garima Khanna, Bhaskara Nand, Jitender M. Khurana
MONATSHEFTE FUR CHEMIE
(2016)
Article
Chemistry, Medicinal
Jayant Sindhu, Harjinder Singh, J. M. Khurana, Jitender Kumar Bhardwaj, Priyanka Saraf, Chetan Sharma
MEDICINAL CHEMISTRY RESEARCH
(2016)
Article
Chemistry, Organic
Sudesh Kumari, Harjinder Singh, Jitender M. Khurana
TETRAHEDRON LETTERS
(2016)
Article
Chemistry, Organic
Harjinder Singh, Garima Khanna, Jitender M. Khurana
TETRAHEDRON LETTERS
(2016)
Article
Chemistry, Physical
Harjinder Singh, Ashima Singh, J. M. Khurana
JOURNAL OF MOLECULAR STRUCTURE
(2017)
Article
Chemistry, Organic
Ashima Singh, Harjinder Singh, J. M. Khurana
TETRAHEDRON LETTERS
(2017)
Article
Chemistry, Physical
Harjinder Singh, M. Rajeshwari, J. M. Khurana
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Harjinder Singh
STRUCTURAL CHEMISTRY
(2019)
Article
Biology
Ashima Singh, Harjinder Singh, J. M. Khurana
COMPUTATIONAL BIOLOGY AND CHEMISTRY
(2019)
Article
Chemistry, Physical
Harjinder Singh
Article
Chemistry, Physical
Harjinder Singh
Summary: This study investigates the crystal structure of 1-(4-chloro-3-nitrophenyl)-6,7-dihydro-1H-benzo[d][1,2,3]triazol-4(5H)-one and predicts its geometry and properties using different basis sets and the DFT method. Non-covalent and intra-molecular interactions are studied, and analyses of electronic structure, vibrational assignments, UV-visible spectra, and chemical reactivity descriptors are performed. Theoretical calculations and comparisons provide insights into the compound's properties and chemical behavior.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Physical
Harjinder Singh, Vaneet Saini
Summary: Pd(II)-catalyzed arylfluorination of disubstituted alkenes was achieved for the synthesis of challenging quaternary fluoro-and hydroxyl sulfonamide substrates. The study investigated the geometrical and electronic properties of the products and demonstrated their potential applications in material science and antibacterial research.
JOURNAL OF MOLECULAR STRUCTURE
(2022)