Article
Chemistry, Multidisciplinary
Md Emdadul Hoque, Ranjana Bisht, Anju Unnikrishnan, Sayan Dey, Mirja Md Mahamudul Hassan, Saikat Guria, Rama Nand Rai, Raghavan B. Sunoj, Buddhadeb Chattopadhyay
Summary: A method of para-selective borylation of aromatic amides is described using a newly designed ligand framework (defa), which shows excellent selectivity and reactivity for the para position. This method can contribute to the development of new catalytic systems and the synthesis of para-functionalized compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Matthew D. Wodrich, Miyeon Chang, Simone Gallarati, Lukasz Wozniak, Nicolai Cramer, Clemence Corminboeuf
Summary: This study creates selectivity and activity maps by analyzing the catalyst-solvent interplay, which can be used to predict and optimize the outcome of competing reactions. The experimental results demonstrate that choosing the appropriate catalyst and solvent can simultaneously optimize catalytic activity and selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Dafydd D. L. Jones, Iskander Douair, Laurent Maron, Cameron Jones
Summary: The study reported the photochemical activation of dimagnesium(I) compounds with inert arenes, leading to high yielding, regioselective reactions. Computational studies suggested that all reactions proceed via photochemically generated magnesium(I) radicals, which reduce the arene substrate before C-H or C-F bond activation processes occur.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Jonathan Martinez-Laguna, Andres Mollar-Cuni, David Ventura-Espinosa, Santiago Martin, Ana Caballero, Jose A. Mata, Pedro J. Perez
Summary: In this study, a novel strategy was developed to functionalize C-H bonds of cyclohexane and benzene with the assistance of nanoparticulated gold catalyst. The catalyst showed exceptional activity and recyclability.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Wang Jiang, Xiuxiu Yang, Lin Lin, Chaoguo Yan, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: Metal-catalyzed C-H activation strategies provide an efficient approach for synthesis. In this study, visible-light-induced late-stage C-H activation was achieved using a single rhodium complex. The reaction offers advantages such as environmental friendliness and the utilization of inherent directing groups, providing a new platform for ligand design and preparation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haidi Tang, Muliang Zhang, Yuchao Zhang, Penghao Luo, Davide Ravelli, Jie Wu
Summary: Researchers have developed a method for synthesizing thioesters through carbonyl thiyl radical-based reactions, using direct photocatalyzed hydrogen atom transfer. This method allows for the synthesis of complex pharmaceutical molecules from readily available commodity chemicals. The study provides a new approach for the application of thiol-ene click chemistry in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Shrikant M. Khake, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports a branch-selective C-H alkenylation method using an iridium catalyst with alkenes, suitable for aniline derivatives containing a pyrimidine-directing group, offering a broad substrate scope and tolerating various functional groups. The origin of branch selectivity was investigated using density functional theory calculations.
Article
Chemistry, Multidisciplinary
Isaac Choi, Antonis M. Messinis, Xiaoyan Hou, Lutz Ackermann
Summary: The research reveals osmaelectrocatalyzed C-H activations using benzoic acids, enabling electrooxidative alkyne annulations with high levels of selectivity. Unprecedented osmium(0) and osmium(II) intermediates were isolated, and detailed mechanistic studies unveiled a facile C-H cleavage and ample substrate scope for annulated heterocycles synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sif T. Linde, Vasco Corti, Vibeke H. Lauridsen, Johannes N. Lamhauge, Karl Anker Jorgensen, Nomaan M. Rezayee
Summary: This article presents a method for obtaining a versatile chiral biaryl structure through C-H halogenation reactions using high-valent Pd catalysis and chiral transient directing groups. The method is scalable, moisture and air insensitive, and in some cases, requires low Pd-loadings of only 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls can be prepared in high yield and excellent stereoselectivity, serving as building blocks for various reactions with orthogonal synthetic handles.
Article
Chemistry, Applied
Mai Yanagawa, Shingo Harada, Shumpei Hirose, Tetsuhiro Nemoto
Summary: The study developed a rhodium-catalyzed C-H functionalization reaction for synthesizing 2,3-fused indole variants using an alpha,beta-unsaturated enone as a directing group and electrophile. This annulation enabled the rapid assembly of valuable hydrocarbazolones from readily available indoles, and computational investigations were conducted to elucidate the reaction pathway and site-selectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Jeffrey Bruffaerts, Inbar Kesten, Keren Buhnik-Rosenblau, Anthony Cohen, Nurit Edri, Morgan Cormier, Yuanfei Zhang, Guo-Ming Ho, Itai Massad, Hila Halfon-Verner, Yechezkel Kashi, Ilan Marek
Summary: A two-step sequential strategy involving a biocatalytic dehydrogenation/remote hydrofunctionalization is reported for selectively converting linear alkanes into valuable functionalized aliphatic derivatives. The dehydrogenation is conducted by a mutant strain of Rhodococcus bacteria, and the resulting alkenes are further functionalized through a metal-catalyzed hydrometalation/migration sequence with various electrophiles. This combined biocatalytic and organometallic approach enables high-yielding site-selective functionalization of unreactive primary C-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jyoti Dhankhar, Micha D. Hofer, Anthony Linden, Ilija Coric
Summary: This article presents a new selectivity mode for C-H arylation reactions, which is the preference for C(sp(2))-H activation next to alkyl groups. The study results indicate that this preference is related to the non-covalent interactions between the catalyst and the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Shaojiang Chen, Akalanka Tennakoon, Kyung-Eun You, Alexander L. L. Paterson, Ryan Yappert, Selim Alayoglu, Lingzhe Fang, Xun Wu, Tommy Yunpu Zhao, Michelle P. P. Lapak, Mukunth Saravanan, Ryan A. A. Hackler, Yi-Yu Wang, Long Qi, Massimiliano Delferro, Tao Li, Byeongdu Lee, Baron Peters, Kenneth R. R. Poeppelmeier, Salai C. C. Ammal, Clifford R. R. Bowers, Frederic A. Perras, Andreas Heyden, Aaron D. D. Sadow, Wenyu Huang
Summary: Non-reducible zirconia catalysts can efficiently hydrogenolytically cleave polyolefins, achieving similar activity as precious metal nanoparticles.
Article
Chemistry, Organic
Teng-Fei Xiao, Yi-Fan Zhang, Wen-Tao Hou, Pen-Ji Yan, Jun Hai, Peng-Fei Xu, Guo-Qiang Xu
Summary: A photoinduced dehydrogenation/(3+2) cycloaddition reaction was reported by combining organic photoredox and Lewis acid catalysis to directly install a benzofuran skeleton on saturated aza-heterocycles. A novel organic photocatalyst, t-Bu-DCQ, with wider redox potential, easy synthesis, and low cost was described, along with the stepwise activation mechanism of dual C(sp(3))-H bonds shown through experimental and computational studies.
Editorial Material
Biochemical Research Methods
Aleksandr Y. Pereverzev, Jana Roithova
JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Chemistry, Physical
Antoine Geoffroy-Neveux, Vanessa Labet, M. Esmail Alikhan
Summary: This study theoretically investigates the mechanism of double proton transfer reaction between pyrazole and guanidine in the presence of an electric field. The results show that the direction of the external electric field affects the mechanism of the double proton transfer, leading to changes in the order and rate of proton transfer. By analyzing the ELF value in the entrance channel, the double proton transfer reaction in the presence of an electric field can be quantitatively anticipated.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Adarsh Koovakattil Surendran, Teun van Wieringen, Deeksha Setia, Cina Foroutan-Nejad, Michal Straka, Lubomir Rulisek, Jana Roithova
Summary: Gold(II) complexes are not commonly used in catalyzing chemical transformations due to their easy oxidation or reduction to more stable gold(III) or gold(I) complexes. In this study, we investigated the thermodynamics, stability, and spectral properties of [Au-II(L)(X)](+) complexes (L=ligand, X=halogen) in the gas phase. It was found that bidentate and tridentate ligands with nitrogen donor atoms are the best choices for stabilizing gaseous [Au-II(L)(X)](+) complexes. Quantum chemical calculations revealed that the molecular and electronic structures, as well as the spectroscopic properties, of the investigated gold(II) complexes are similar to those of stable copper(II) complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Bernard Silvi, Esmail Alikhani
Summary: Partitioning atomic and molecular charge densities in non-overlapping chemically significant regions is a challenging problem for quantum chemists. This method aims to determine boundaries using statistical methods or information theory.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Biochemical Research Methods
Guilherme L. Tripodi, Jana Roithova
Summary: This study investigates the application of ArIO as an oxidant for FeII species, revealing its oxidation mechanism and reaction properties, providing theoretical guidance for the design and synthesis of related reactions.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Chemistry, Multidisciplinary
Karolina Kwapien, Eva Nittinger, Jiazhen He, Christian Margreitter, Alexey Voronov, Christian Tyrchan
Summary: This study examines the predictability of four properties relevant for drug design using different data sets and machine learning algorithms. The study confirms that additive data are the easiest to predict, highlighting the complexity of predicting nonadditive events in drug design.
Article
Chemistry, Inorganic & Nuclear
Rob Bakker, Abhinav Bairagi, Monica Rodriguez, Guilherme L. Tripodi, Aleksandr Y. Pereverzev, Jana Roithova
Summary: Cobalt(III)peroxo complexes were studied to investigate the effect of hydrogen bonding on the O2 binding energy and the O-O bond activation. The results showed that hydrogen bonding stabilized the cobalt(III)peroxo core by 10-20 kJ mol-1. The introduction of the first amino group had the largest stabilization effect, while additional amino groups did not significantly change the results. The amino group could transfer a hydrogen atom to the peroxo ligands, leading to O-O bond cleavage with thermodynamic favorability but entropic disfavorability.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yujeong Lee, Guilherme L. Tripodi, Donghyun Jeong, Sunggi Lee, Jana Roithova, Jaeheung Cho
Summary: A high-valent manganese(IV)-hydroxo complex was synthesized and characterized in this study. It was found that this complex can activate C-H bonds of aliphatic and aromatic compounds under mild conditions. Detailed kinetic studies revealed that the activation of C-H bonds occurs via rate-determining hydrogen atom abstraction and electron-transfer pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Monica Rodriguez, Aleksandr Y. Pereverzev, Jana Roithova
Summary: A novel octahedral non-heme iron-acyl-nitrenoid complex was presented, and its reactivity was studied using a flow chemistry setup with online mass spectrometry detection. It was found that the iron-acyl-nitrenoid complex can activate C-H bonds via hydrogen-atom transfer and form new N-S bonds in the reaction with thiophenol. However, the reaction with hydrocarbons results in the activation of C-H bonds without a subsequent rebound process.
Article
Chemistry, Multidisciplinary
Erik Andris, Michal Straka, Jan Vrana, Ales Ruliska, Jana Roithova, Lubomir Rulisek
Summary: Gold(I) centers can form moderately strong (Au...H) hydrogen bonds with tertiary ammonium groups, but similar hydrogen bonding interactions with isoelectronic silver(I) or copper(I) centers are unknown. The replacement of Cl with Br or I in 3AuCl(+) had only a small effect on the Au...H bond strength. Experimental and computational results showed that the Ag...H and Cu...H interactions were only marginal in the complexes studied, while a Cl...H hydrogen bond was formed. However, when less flexible ligands were used, the presence of Ag...H and Cu...H hydrogen bonds with similar strength to the Au...H bond in 3AuCl(+) was predicted.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Jana Roithova
Summary: Copper(II) complexes with N-oxyl reagents like TEMPO can selectively oxidize alcohols to aldehydes or ketones. Intermediate copper complexes were theoretically studied but never experimentally detected. This study presents an analysis of frozen intermediates containing alcohols lacking α-hydrogen atoms, preventing oxidation.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Aleksandr Y. Pereverzev, Corentin Rossi, Jana Roithova
Summary: The search for chemical structures responsible for diffuse interstellar bands remains a major challenge in astrochemistry, requiring experimental verification of structures obtained under laboratory conditions. In this study, we demonstrate the isomerization of the doubly charged polyaromatic hydrocarbon phenanthrene obtained through electron ionization. Our results show that the phenanthrene dication has a broad visible spectrum, making it unsuitable for diffuse interstellar band search. We also observe the isomerization of phenanthrene dication during the ionization process, leading to the detection of another C14H102+ isomer.
Article
Chemistry, Physical
Sreekanta Debnath, Alexander Schaefer, Karolina A. Haupa, Dmitry Strelnikov, Jana Roithova, Juraj Jasik, Sergei Lebedkin, Manfred M. Kappes
Summary: Helium tagging photodissociation action spectroscopy and laser-induced fluorescence spectroscopy in neon matrix were used to study the photophysics of electrosprayed rhodamine B cation at low temperatures. The experiments were conducted using He-TAG apparatus for helium tagging and Depo-II machine for LIF measurements. The resulting electronic spectra provide benchmarks for theoretical description of this organic dye.
Article
Chemistry, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Quentin Duez, Guilherme L. Tripodi, Magda M. J. Dekker, Jiangkun Ouyang, Kais Dhbaibi, Nicolas Vanthuyne, Jeanne Crassous, Jana Roithova, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: The kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cage compounds is determined by the planar chirality of the host and influenced by its size, but not the chirality of its substituents.
CHEMICAL COMMUNICATIONS
(2023)