Article
Chemistry, Organic
Xiao-Xiao Li, Jian-Sen Wang, Xiao-Xia You, Rong-Lin Zhong, Zhong-Min Su
Summary: The Pd-catalyzed borylation of fluorobenzene was investigated theoretically, and it was found that the reaction proceeds through an unprecedented 3 + 6-membered ring transition state. This transition state involves the interaction of one LiHMDS as a ligand and another LiHMDS providing essential Li·N and Li·F interactions, effectively overcoming the destabilization caused by the distortion of the phenyl-F bond.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hsuan-Hung Liao, Shao-Chi Lee, Hsin Kao, Yu-Ling Hsu, Che-Ming Hsu, Yong-Ting Tsao, Shinje Minoza, Li-Yun Li, Zong-Nan Tsai, Kuei-Chen Chang, Cheng-Ku Cheng, Cheng-Lin Chan, Yi-Sian Chien, Cheng-chau Chiu
Summary: This article presents a new method for synthesizing perfluoroaryl sulfides, which can be conducted at ambient conditions or as industrial processes, with a wide tolerance for various functional groups. The reaction mechanism involves a nucleophilic attack of a thiol group on an electron-poor aromatic ring, with a predicted stepwise or concerted mechanism.
CELL REPORTS PHYSICAL SCIENCE
(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, Physical
Hayden T. Robinson, Timothy R. Corkish, Christian T. Haakansson, Peter D. Watson, Allan J. McKinley, Duncan A. Wild
Summary: Mass spectrometry and anion photoelectron spectroscopy were used to study the gas-phase SN2 reaction involving Br- and CH3I. The anion photoelectron spectra associated with the reaction intermediates were presented. High-level CCSD(T) calculations were utilized to investigate the reaction intermediates and rationalize the photoelectron spectra.
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, Organic
Komal Mittal, Ashley V. Pham, Amanda G. Davis, Abigail D. Richardson, Clement De Hoe, Ryan T. Dean, Vi Baird, Ashley Ringer McDonald, Derik K. Frantz
Summary: At elevated temperatures, a strained, cyclic meta-quaterphenylene acetylene undergoes an intramolecular cyclization reaction to form benz[e]indeno[1,2,3-hi]acephenanthrylene. This reaction represents a Diels-Alder reaction at the 2-, 1-, 1 '-, and 2 '-positions of a biphenyl derivative, similar to the bay regions of perylene and other periacenes. Kinetics studies reveal that the reaction has a similar energy barrier to a concerted [4 + 2]-cycloaddition.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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
Engineering, Chemical
Fan Zhang, Fan Yang, Zhihong Ma, Ling Zhao, Weizhong Zheng, Weizhen Sun
Summary: In this study, the effects of alkyl chain length of the substrate on the reaction kinetics and microdynamics between MIm and RSCN were analyzed. Experimental and simulation results showed that longer chain lengths of thiocyanate resulted in slower rate constants and higher activation energies. The insights from this work could guide the industrial synthesis of ILs.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(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.
Article
Chemistry, Multidisciplinary
Dirk Schlueter, Florian Kleemiss, Malte Fugel, Enno Lork, Kunihisa Sugimoto, Simon Grabowsky, Jeffrey R. Harmer, Matthias Vogt
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Axel Haupt, Daniel Duvinage, Enno Lork, Maksym Ponomarenko, Gerd-Volker Roeschenthaler
Summary: This study describes the preparation of silver(I) pentafluorooxosulfate from commercially available AgF and OSF4, which surprisingly shows stability in a MeCN solution. Additionally, the stabilisation of AgOSF5 with 2,2'-bipyridine ligands has enabled the transfer of OSF5 groups to aryne moieties, providing a new and safe method for preparing OSF5-substituted arenes. X-ray crystal structure analysis of transition-metal OSF5 compounds reveals distorted octahedral [OSF5](-) anions stabilised by hydrogen bonding.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Martin Hejda, Daniel Duvinage, Enno Lork, Antonin Lycka, Zdenck Cernosek, Jan Machacek, Sergey Makarov, Sergey Ketkov, Stefan Mebs, Libor Dostal, Jens Beckmann
Summary: The aryltellurenyl cation and the weakly coordinating carborane anion form an isolable ion pair complex, in which the Bronsted acidity of the formally hydridic B-H bonds is dramatically increased, leading to a proton transfer reaction at slightly elevated temperatures. The isolation of zwitterionic isomers further confirms the electrophilic activation of B-H bonds in the carborane moiety.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Oleg O. Shyshkov, Alexander A. Kolomeitsev, Berthold Hoge, Enno Lork, Axel Haupt, Mira Kessler, Gerd-Volker Roeschenthaler
Summary: Phosphoranides are hypervalent species that can serve as model compounds for intermediates or transition states in nucleophilic substitution reactions. This study reports the syntheses and properties of stable trifluoromethylphosphoranide salts, and investigates their reactivity towards electrophiles. The structures and dynamics of these compounds are determined using X-ray crystallography and NMR spectroscopy.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Felix Feige, Jeen Al-Issa, Julius F. Kogel, Enno Lork, Elena Rychagova, Sergey Ketkov, Jens Beckmann
Summary: The reaction between sodium salts of perfluorinated tertiary alcohols and SiCl4 resulted in the formation of di-substituted dichlorosilanes and corresponding silanediols, which are stable towards self-condensation at ambient conditions. Similar compounds, disiloxanes, were also prepared in a similar manner.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Julius F. Koegel, Felix Feige, Daniel Duvinage, Enno Lork, Alexey Y. Timoshkin, Jens Beckmann
Summary: In this article, we investigate the structural motifs of sodium, magnesium, zinc, titanium, silver and thallium complexes based on perfluorinated trityl alcohol. We found that these complexes exhibit different structural features, and metal fluorine contacts play an important role in these structures.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Daniel Duvinage, Marvin Janssen, Enno Lork, Hansjoerg Gruetzmacher, Stefan Mebs, Jens Beckmann
Summary: By employing bulky m-terphenyl substituents for kinetic stabilization, the isolation of diarylantimony and diarylbismuth phosphaethynolates was achieved. The structures of these compounds were fully characterized crystallographically and spectroscopically, and further analyzed using DFT methods.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Inorganic & Nuclear
Daniel Duvinage, Marvin Janssen, Enno Lork, Hansjoerg Gruetzmacher, Stefan Mebs, Jens Beckmann
Summary: The synthesis and reactivity of heavier group 13 phosphaketene complexes were investigated and characterized. The electronic structure analysis revealed distinct bonding characteristics of the PCO fragment in these compounds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Farzin Mostaghimi, Daniel Duvinage, Enno Lork, Jens Beckmann
Summary: Compound 3 was synthesized by the condensation of 4,4'-dimethyldiphenylether with tellurium tetrachloride, and characterized by X-ray diffraction. Compared to the parent phenoxatellurine (1) and the 10,10,-dichlorophenoxatellurine (2), 3 exhibits a planar ring structure.
MAIN GROUP METAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Yannik Appiarius, Tim Stauch, Enno Lork, Pascal Rusch, Nadja C. Bigall, Anne Staubitz
Summary: A convergent synthetic route towards boron-nitrogen containing polycyclic aromatic hydrocarbons (BN-PAHs) was developed, allowing the synthesis of six derivatives with high quantum yields. The route avoids the need for substituted PAH precursors and instead builds up BN-PAHs solely from easily accessible monocycles. The emission properties of the derivatives were dependent on the connectivity of the rings, and one derivative exhibited significantly redshifted emission due to excimer formation.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Materials Science, Multidisciplinary
Nadi Eleya, Souvik Ghosh, Enno Lork, Anne Staubitz
Summary: A new switchable azobenzene macrocyclic derivative with high yield and unique photoisomerization properties has been synthesized, showing promising applications in data storage and solar fuels.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Sinas Furan, Emanuel Hupf, Enno Lork, Jens Beckmann
REVUE ROUMAINE DE CHIMIE
(2020)
Article
Chemistry, Multidisciplinary
Isabel-Maria Ramirez y Medina, Markus Rohdenburg, Enno Lork, Anne Staubitz
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Inorganic & Nuclear
Sebastian Holsten, Emanuel Hupf, Enno Lork, Stefan Mebs, Jens Beckmann
DALTON TRANSACTIONS
(2020)
Article
Chemistry, Inorganic & Nuclear
Farzin Mostaghimi, Enno Lork, Jens Beckmann
MAIN GROUP METAL CHEMISTRY
(2020)
