Article
Chemistry, Applied
Christoph Zippel, Zahid Hassan, Ahmad Qais Parsa, Jens Hohmann, Stefan Braese
Summary: A kinetic resolution method was developed to obtain enantiomerically pure PCP derivatives through ruthenium-catalyzed enantioselective hydrogenation, providing important intermediates for the synthesis of chiral materials and catalysts.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Shiru Yuan, Chen Liao, Wen-Hua Zheng
Summary: In this study, planar chiral [2.2]paracyclophane-based isothiourea catalysts were synthesized in a few simple steps with high yields. These catalysts showed highly efficient catalytic enantioselective fluorination of carboxylic acids, providing a broad range of optically active alpha-fluoroesters in high yield and excellent enantioselectivity.
Article
Chemistry, Multidisciplinary
Wei Gong, Haomiao Xie, Karam B. Idrees, Florencia A. Son, Zhijie Chen, Fanrui Sha, Yan Liu, Yong Cui, Omar K. Farha
Summary: The sorption of water vapor by metal-organic frameworks (MOFs) has attracted significant attention due to its potential applications in various areas. In this study, a series of robust Zr-MOFs based on a unique [2.2]paracyclophane (PCP) scaffold were designed using reticular chemistry. The water vapor sorption performances of these Zr-MOFs were found to be highly dependent on their framework topology and pore metric, with two Zr-MOFs exhibiting high uptake capacities and excellent working capacity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jules Brom, Antoine Maruani, Serge Turcaud, Sonia Lajnef, Fabienne Peyrot, Laurent Micouin, Erica Benedetti
Summary: The study demonstrates the photocatalytic activity of coumarins derived from [2.2]paracyclophane for the reductive cleavage of sulfonamides under light-irradiation. The findings open up new possibilities for the application of pCps in photocatalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sundaravel Vivek Kumar, Patrick J. Guiry
Summary: We have developed a facile synthetic route for a novel series of imidazolinyl-[2.2]paracyclophanol (UCD-Imphanol) ligands with central and planar chirality. These ligands showed excellent activities and selectivities in asymmetric reactions, leading to enantioenriched pyrrolidines with high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yang Zhao, Yi-Xuan Ding, Bo Wu, Yong-Gui Zhou
Summary: Nickel-catalyzed asymmetric hydrogenation was successfully utilized for the kinetic resolution of cyclic N-sulfonylimines derived from [2.2]paracyclophane. High selectivity factors were observed, leading to good yields and high levels of enantiopurity in the recovered materials and hydrogenation products, which are valuable synthetic intermediates for planar chiral [2.2]paracyclophane-based compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yong Yuan, Xue Liu, Jingcheng Hu, Pengjie Wang, Shengchun Wang, Hesham Alhumade, Aiwen Lei
Summary: In this study, a facile and novel electrochemical method was developed for the synthesis of tertiary phosphines with excellent yields. The protocol showed good reaction selectivity and scalability.
Article
Chemistry, Physical
Connor S. MacNeil, Hongyu Zhong, Tyler P. Pabst, Michael Shevlin, Paul J. Chirik
Summary: The cobalt-catalyzed asymmetric hydrogenation of dehydro-sitagliptin was studied and applied to the synthesis of sitagliptin. The discovery of catalysts was accelerated by the synthesis of cationic bis(phosphine) cobalt eta 6-arene complexes. The optimal catalyst showed high yield and enantioselectivity, and maintained excellent activity and selectivity after standing in air for 2 weeks.
Article
Chemistry, Multidisciplinary
Motonori Watanabe, Yuka Ono, Tatsumi Ishihara, Yuan Jay Chang, Masahiko Shibahara
Summary: Novel donor-acceptor dyads were synthesized and used to fabricate dye-sensitized hydrogen production systems. The [2.2]PCP moiety exhibited stronger electron-donating properties compared to the [3.3]PCP moiety, resulting in effective charge transfer and hydrogen generation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Tae Wan Kim, Hwiram Jeong, Dongun Kim, Yeongin Jo, Hwi Ju Jung, Ji Hoon Park, Young-Woong Suh
Summary: This study investigates the impacts of CH4 fraction on the essential steps for liquid organic hydrogen carrier systems. The results show that a CH4 fraction higher than 30% negatively affects the carbon content and catalytic activity, but has less impact under mild conditions.
JOURNAL OF POWER SOURCES
(2022)
Article
Chemistry, Physical
Bin Wang, Pei-ya Li, Qian Dong, Li-qin Chen, Hai-qiang Wang, Pei-long Han, Tao Fang
Summary: This paper discusses the preparation of four kinds of Ni/Co bimetallic catalysts and their effects on the hydrogenation performance of NEC. The results show that the addition of 50% cobalt achieves the most significant hydrogenation activity, with 100% NEC conversion and 98.99% 12H-NEC selectivity. The catalyst exhibits a hydrogenation capacity of 5.77 wt % at a reduction temperature of 450 degrees C. The synergistic interaction between Ni/Co metals is identified as the key factor for the remarkable catalytic activity. The development and application of highly efficient nonprecious metal hydrogenation catalysts contribute to the commercialization of LOHC technology.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Bin Wang, Pei-ya Li, Qian Dong, Li-qin Chen, Hai-qiang Wang, Pei-long Han, Tao Fang
Summary: This paper prepared four kinds of Ni/Co bimetallic catalysts with different proportions by the impregnation method. The effects of the Ni/Co molar ratio and the reduction temperature on the hydrogenation performance of N-ethylcarbazole (NEC) were studied. The design and application of highly efficient nonprecious metal hydrogenation catalysts provide more feasibility to promote the commercial development of liquid organic hydrogen carrier technology.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yaoyu Liang, Jie Luo, David Milstein
Summary: In this study, a new reaction of acceptorless dehydrogenative coupling of epoxides and amines to form amides catalyzed by ruthenium pincer complexes is reported. This reaction shows high yield and selectivity, and is significant in various academic and industrial fields.
Article
Multidisciplinary Sciences
Xinzhe Tian, Yinggang Guo, Wankai An, Yun-Lai Ren, Yuchen Qin, Caoyuan Niu, Xin Zheng
Summary: The coupling of light-induced oxidative half-reaction of water splitting with reduction of organic compounds provides a pollutive reductant-free method for synthesizing biaryl skeletons. The use of green visible-light energy endows this process with advantages including mild conditions and good functional group tolerance.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Dandan Lu, Weidong Lin, Feng Su, Kongchuan Wu, Ting-Bin Wen, Hui-Jun Zhang
Summary: In this study, a series of SPO-RhIII complexes relevant to RhIII-catalyzed C-H phosphorylation were isolated and characterized. The research on their reactivities in C-H rhodation revealed the crucial role of a suitable base in reducing RhIII deactivation by SPOs. Finally, an efficient RhIII-catalyzed aryl C-H phosphorylation with diarylphosphine oxides was developed using silver carbonate as both a base and an oxidant.
Article
Polymer Science
Peng Hou, Peter Oechsle, Dirk Kuckling, Jan Paradies
MACROMOLECULAR RAPID COMMUNICATIONS
(2020)
Article
Nanoscience & Nanotechnology
Jie Li, Chendong Ji, Baozhong Lu, Maksim Rodin, Jan Paradies, Meizhen Yin, Dirk Kuckling
ACS APPLIED MATERIALS & INTERFACES
(2020)
Article
Chemistry, Multidisciplinary
Laura Koering, Nikolai A. Sitte, Markus Bursch, Stefan Grimme, Jan Paradies
Summary: The metal-free catalytic hydrogenation of secondary carboxylic acid amides is achieved through two new catalytic reactions, involving the conversion of amides into imidoyl chlorides and the subsequent hydrogenation of the generated chlorides by an FLP-catalyst. Mechanistic and quantum mechanical calculations support the unique role of chloride as a Lewis base in FLP-mediated H-2-activation during the hydrogenation process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Andrei Gurinov, Benedikt Sieland, Andrey Kuzhelev, Hossam Elgabarty, Thomas D. Kuehne, Thomas Prisner, Jan Paradies, Marc Baldus, Konstantin L. Ivanov, Svetlana Pylaeva
Summary: A novel set of polarizing agents - mixed-valence compounds have been investigated through theoretical and experimental methods, showcasing their performance in high-field dynamic nuclear polarization (DNP) NMR experiments in the solid state. These compounds, with molecular mobility persisting even in solids, can be used to conduct Overhauser-DNP experiments in the solid state, providing favorable conditions for dynamic nuclear polarization formation at ultra-high magnetic fields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Garrit Wicker, Roland Schoch, Jan Paradies
Summary: The borane-catalyzed synthesis of dihydroquinoline-4-ones has been developed, with high yields and excellent diastereoselectivity. The reaction mechanism is investigated through kinetic, isotope labeling, and computational experiments.
Article
Chemistry, Organic
Rundong Zhou, Jan Paradies
Summary: The borane catalyzed redox isomerization of 2-amino chalcones was successfully developed, leading to the synthesis of tetrahydroquinolines in high yields as a mixture of cis/trans diastereomers. The investigation into the reaction mechanism revealed that the reaction proceeds through a concerted [1,5] hydride shift mechanism, distinct from borane-mediated C(sp(3))-H hydride abstraction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Laura Koering, Nikolai A. Sitte, Jan Paradies
Summary: The paper reviews the development of frustrated Lewis pair catalyzed hydrogenation of tertiary and secondary amides, as well as strategies to overcome challenges in the reaction development process. Furthermore, the chemistry is extended to the hydrogenation of polyamides and trifluoroacetamides for the introduction of trifluoroethyl groups into organic molecules.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Garrit Wicker, Rundong Zhou, Roland Schoch, Jan Paradies
Summary: The stereospecific sigmatropic carbon shift of C3 ammonium enolates has been discovered. According to mechanistic, kinetic, and computational experiments, this rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza-Michael addition. The reaction produces tetrahydroquinoline-4-ones with excellent diastereoselectivities and high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng Hou, Sebastian Peschtrich, Nils Huber, Wolfram Feuerstein, Angela Bihlmeier, Ivo Krummenacher, Roland Schoch, Wim Klopper, Frank Breher, Jan Paradies
Summary: This study presents the synthesis and characterization of a series of quinoid sulfur-containing imidazolyl-substituted heteroacenes. The optoelectronic and magnetic properties of these compounds were investigated using various spectroscopic techniques and quantum-chemical calculations, and compared to their benzo congeners.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Benedikt Sieland, Axel Hoppe, Arne J. Stepen, Jan Paradies
Summary: A frustrated Lewis pair-catalyzed hydroboration of aromatic and aliphatic nitriles was developed, providing primary amines in high yields with low catalyst loading. The reaction exhibits high functional group tolerance and Z-selectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Laura Koering, Arne Stepen, Bernhard Birenheide, Simon Barth, Maxim Leskov, Roland Schoch, Felix Kraemer, Frank Breher, Jan Paradies
Summary: A series of redox-responsive ferrocenyl-substituted boranes and boronic esters were synthesized, and the oxidation of the ferrocenyl ligand to the ferrocenium increased the Lewis acidity beyond the strength of SbF5. This was investigated experimentally and computationally, and the resulting highly Lewis acidic boron compounds were used for catalytic C-F and S-F bond activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peng Hou, Sebastian Peschtrich, Wolfram Feuerstein, Roland Schoch, Stephan Hohloch, Frank Breher, Jan Paradies
Summary: The synthesis of three new imidazolyl-substituted sulfur-containing heteroacenes is presented. These heteroacenes, composed of annelated benzo- and naphthothiophenes, serve as precursors for the generation of open-shell quinoid heteroacenes through oxidation with alkaline ferric cyanide. Spectroscopic and computational experiments provide evidence for the formation of reactive open-shell quinoids, which rapidly transform into paramagnetic polymeric materials.
Article
Chemistry, Organic
Rundong Zhou, Zoleykha Pirhadi Tavandashti, Jan Paradies
Summary: In recent years, frustrated Lewis pairs have been extensively used for activating small molecules and catalytic transformations. This graphical review aims to provide a fundamental understanding of frustrated Lewis pair reactivity and its exploitation in catalytic reactions.
Review
Chemistry, Multidisciplinary
Jan Paradies
Summary: Metal-free hydrogenation through the activation of molecular hydrogen by main-group element catalysts, known as frustrated Lewis pairs, has emerged as an alternative to transition metal catalysis. However, the understanding of the structure-reactivity relationship is less developed compared to transition metal complexes. In this Account, the correlation between Lewis acidity, Lewis basicity, and reactivity is discussed, along with the systematic study of frustrated Lewis pairs in various reactions. These studies have led to the development of qualitative and quantitative structure-reactivity relationships in imine hydrogenations and the discovery of new catalytic systems for the hydrogenation of nitroolefins, acrylates, malonates, amines, aza-heterocycles, and deoxygenation of phosphane oxides and carboxylic acid amides.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Fabian A. Watt, Benedikt Sieland, Nicole Dickmann, Roland Schoch, Regine Herbst-Irmer, Holger Ott, Jan Paradies, Dirk Kuckling, Stephan Hohloch
Summary: Two rigid mesoionic carbene (MIC) ligands were synthesized via intramolecular Finkelstein cyclisation, and their coordination behavior towards nickel(s) acetate was investigated. Despite minor differences in chemical composition, the nickel(s) carbene complexes showed curious differences in chemical properties, and their potential in coupling reactions was evaluated.
DALTON TRANSACTIONS
(2021)
