Article
Chemistry, Multidisciplinary
Muriel Durandetti
Summary: The direct formation of C-C bonds catalyzed by nickel complexes has become an important research topic in the past fifty years, and has recently seen a resurgence as a new area in nickel chemistry. This paper provides a summary of the use of nickel complexes in catalysis and highlights the evolution of the authors' own research.
Review
Chemistry, Multidisciplinary
Yan-Long Zheng, Stephen G. Newman
Summary: This article discusses two common families of chemical reactions - cross-coupling reactions and pi bond addition reactions - and the significant overlap between them. Recent advancements in catalysis have revealed the role of compounds such as esters, aldehydes, and alcohols in nickel- and palladium-catalyzed reactions, offering promising alternatives for the preparation of amides, ketones, substituted alcohols, alkanes, and more. The focus is on the key mechanistic steps that allow these non-traditional substrates to be incorporated into cross-coupling-like catalytic cycles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Denis D. Borisov, Roman A. Novikov, Yury Tomilov
Summary: The reactions of styrylmalonates with aromatic aldehydes in the presence of Lewis and Bronsted acids, along with their regularities, have been studied in detail. Various approaches have been developed for the synthesis of polysubstituted compounds with control over chemo-, regio-, stereo-, and diastereoselectivity. The mechanisms of these reactions were extensively studied using multinuclear NMR experiments, monitoring reactions in NMR tubes, and O-18 isotope labeling.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Pannan Miao, Ruining Li, Xianfeng Lin, Liangming Rao, Zhankui Sun
Summary: Cascade reactions are efficient and environmentally friendly methods for constructing multiple carbon-carbon bonds in one step. This method involves a relay olefination and radical addition process induced by visible light, offering mild conditions, robustness, and excellent functionality compatibility. The synthetic utility of this approach is demonstrated by a two-step synthesis of indolizidine 209D.
Article
Chemistry, Multidisciplinary
Zhenghong Zhou, Jimin Yang, Bo Yang, Yang Han, Lijuan Zhu, Xiao-Song Xue, Feng Zhu
Summary: This study presents a pioneering example of nickel-catalysed enantioconvergent Stille cross-coupling reactions. The reactions result in the formation of C-C bonds in good to high yields with excellent stereoselectivity, providing a practical and cost-effective method for synthesis. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process, opening up new research possibilities in the field of Stille reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Huiping Yin, Tianjiao Huang, Bai Shi, Wei Cao, Chenxia Yu, Tuanjie Li, Kai Zhang, Changsheng Yao
Summary: A practical, convenient, and facile method for constructing highly functionalized 2-pyrrolidinone has been developed using N-heterocyclic carbene (NHC)-catalyzed radical tandem cyclization (30 examples, up to 94% yield). The method is transition metal-free and exhibits broad substrate scope, excellent functional group compatibility, and high efficiency.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Shuangrong Liu, Zhimin Ying, Qi Zhu, Xiuwen Zhong, Jie Cen, You Wu, Yongping Yu, Jiaan Shao, Wenteng Chen
Summary: This study reveals a step-economical nitrite-triggered cycloaddition reaction for the modular assembly of isoxazoles (or isoxazolines) from bromide and alkyne/alkene. The reaction offers high regio-selectivity, excellent efficiency, wide functionality tolerance, biocompatible conditions, and operational simplicity, making it suitable for the direct diversification of pharmaceuticals and bio-relevant motifs.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Chao Yang, Dong-Ting Dai, Huan-Xuan Lu, Feng-Lian Zhang, Yao Fu, Yun-He Xu
Summary: Unprecedented palladium-catalysed regio- and stereo-selective coupling reactions of homoallenylboronates with various reactants in aqueous solution resulted in high yields of products with specific stereoselectivity, demonstrating the potential of homoallenylboronates as powerful and flexible platform molecules for the formation of complex 1,3-dienyl compounds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Biochemistry & Molecular Biology
Jakub Adamek, Miroslawa Grymel, Anna Kuznik, Agnieszka Pazdzierniok-Holewa
Summary: N-acyliminium-type cations are highly reactive intermediates used in organic synthesis, generated in situ with acidic catalysts. This review highlights the unique properties and wide applications of 1-aminoalkyltriarylphosphonium derivatives, and discusses their prospects and limitations in synthesis and medicinal chemistry.
Article
Chemistry, Physical
Dominik Birnthaler, Rok Narobe, Eliseo Lopez-Berguno, Christoph Haag, Burkhard Koenig
Summary: Ligand-to-metal charge transfer (LMCT) photo-catalysis enables the activation and utilization of halides and other heteroatoms in metal complexes. The application of bismuth LMCT in organic radical coupling reactions has been expanded, generating chlorine and carboxyl radicals in net-oxidative and redox-neutral photochemical reactions. The study reveals BiCl4- and BiCl52- as the catalytically active bismuth species under 385 nm irradiation, providing insight into the reactivity of the highly reactive bismuth(II) catalyst fragment through cyclic voltammetry and UV-vis studies.
Article
Chemistry, Organic
Hong Li, Rongqiang Tian, Zheng Duan
Summary: A facile and highly atom-economic approach to 2-phosphafurans was reported in this study, with the key step utilizing the Lewis acidity of electrophilic phosphinidenes to induce an intramolecular cyclization with enones. Dearomative hetero-Diels-Alder reactions of 2-phosphafurans provided two series of bicyclic phosphacycles, representing a rare synthetic application of the Lewis acidity of electrophilic phosphinidene complexes in phosphinidene chemistry.
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Multidisciplinary
Diego Madronero, Cesar A. Mujica-Martinez, Alfredo Vazquez
Summary: Lithium anions derived from O-carbonate-protected cyanohydrins undergo conjugate addition to cycloalkenones with the concomitant transfer of the alkoxycarbonyl group to produce tricarbonyl compounds. These products offer various possibilities for further development, as demonstrated by the formation of bicyclic and tricyclic systems through intramolecular condensation reactions.
Article
Chemistry, Multidisciplinary
Anna Arkhypchuk, Nicolas D'Imperio, Jordann A. L. Wells, Sascha Ott
Summary: This article presents a new strategy for the reductive coupling of carbonyl compounds to alkenes, using a [2 + 2] cycloaddition reaction to efficiently produce tetraaryl-substituted alkenes. This method offers a promising alternative to the McMurry coupling and enables the formation of unusual macrocycles without the need for high dilution conditions or templating.
Review
Biochemistry & Molecular Biology
Gheorghe Ilia, Vasile Simulescu, Nicoleta Plesu, Vlad Chiriac, Petru Merghes
Summary: Carbonyl olefinations are important organic syntheses for forming C=C bonds, often with high yields and excellent stereoselectivity. The Wittig reaction is a well-known carbonyl olefination method, involving the reaction between an aldehyde or ketone and a Wittig reagent. The use of ultrasound in these reactions, including modified Wittig syntheses, has been studied for green synthesis and improved yields and reaction times.
Article
Chemistry, Multidisciplinary
Finn Schulz, Philipp Ehni, Bianca Wank, Alina Bauer, Wolfgang Frey, Sabine Laschat
Summary: By studying the self-assembly process of 6-alkoxy-2-bromoazulenes, insights into the unique electronic properties of azulene derivatives and the formation mechanism of liquid crystal phases were obtained. A comparison of experimental data and quantum chemical calculations revealed significant differences in molecular polarity, affecting optical and mesomorphic properties, leading to the design of novel thin-film devices.
Article
Chemistry, Organic
Max Deimling, Anna Zens, Natja Park, Christine Hess, Simon Klenk, Zarfishan Dilruba, Angelika Baro, Sabine Laschat
Summary: Functionalized hydropentalenes are important building blocks for natural products and asymmetric catalysis ligands. The assembly and functionalization of this convex roof-shaped scaffold is challenging and has motivated various synthetic approaches, including the author's contributions.
Article
Chemistry, Physical
Max Deimling, Shravan R. Kousik, Karina Abitaev, Wolfgang Frey, Thomas Sottmann, Kaloian Koynov, Sabine Laschat, Petia Atanasova
Summary: The study used macro-mesoporous silica inverse opal films as a model system to investigate the molecular infiltration behavior of a probe molecule. The results showed homogeneous tracer distribution in the SiO2-IO films and attachment to both transport and mesopores.
Article
Chemistry, Organic
Andrea Buehlmeyer, Philipp Ehni, Dustin Ullmann, Wolfgang Frey, Angelika Baro, Sabine Laschat
Summary: The Fischer indole reaction of Weiss diketone with 4-bromophenylhydrazine yielded the key intermediate 2,8-dibromo-hexahydropentaleno[2,1-b:5,4-b']diindole, which was further converted to the target compounds by N-protection/Suzuki cross-coupling. Variations in protecting groups and alkoxy chain lengths influenced the mesomorphic properties of the phenyl diindoles, with specific derivatives forming enantiotropic mesophases. Chain lengths determined the mesophase range and type, with shorter chains resulting in nematic phases and longer chains leading to additional smectic phases. Crystal structure analysis revealed perpendicular orientations of the indole/biphenyl parts due to the folding angle of the hydropentalene core.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jakob Knelles, Chris Wanner, Finn Schulz, Marcel Freund, Mohamed A. Kolmangadi, Angelika Baro, Patrick Huber, Andreas Schoenhals, Sabine Laschat
Summary: The study found that only hydrazones synthesized under certain conditions displayed hexagonal columnar mesophases, while all other derivatives were non-mesomorphic, even in the presence of H-bonds. Dipole moments of nitro-substituted hydrazones play a key role in mesophase formation, which is further supported by intramolecular H-bonding.
Article
Chemistry, Organic
Nicole Schaedel, Esra Icik, Maike Martini, Luca Altevogt, Isabell Ramming, Andreas Greulich, Angelika Baro, Ursula Bilitewski, Sabine Laschat
Summary: Amino acid derivatives with a central cationic heterocyclic core, such as imidazolium, were synthesized and investigated for their biocompatibility in this study. The compounds were synthesized from imidazole or histidine via N-alkylation using aspartate- and glutamate-derived mesylates as a key step.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Moritz Sinast, Birgit Claasen, Yannick Stoeckl, Andreas Greulich, Anna Zens, Angelika Baro, Sabine Laschat
Summary: A new approach has been developed for the synthesis of key structures of the clifednamide family with high yield and enantiomeric excess, offering a potential pathway for key intermediates in the clifednamide biosynthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kerstin Truebe, Andrea Buehlmeyer, Finn Schulz, Marco Andre Grunwald, Anna Zens, Angelika Baro, Sabine Laschat
Summary: Novel hockey-stick-shaped mesogens were synthesized using tricyclic bromoindoles as intermediates. Different substituents were studied for their impact on the mesomorphic phases, and elongation of the molecular structure led to liquid crystalline hockey sticks with monotropic nematic phases. Introduction of an N-methyl-imidazolium head group also resulted in new hockey stick ionic liquid crystals.
Article
Chemistry, Multidisciplinary
Max Ebert, Irene Carrasco, Noee Dumait, Wolfgang Frey, Angelika Baro, Anna Zens, Matthias Lehmann, Gregory Taupier, Stephane Cordier, Emmanuel Jacques, Yann Molard, Sabine Laschat
Summary: Research on red-NIR emissive hybrid materials obtained with phosphorescent octahedral molybdenum cluster anions associated with amphiphilic guanidinium minidendrons shows a correlation between the structural hierarchy and emission performance.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Manuel Kirchhof, Karina Abitaev, Abdulwahab Abouhaileh, Katrin Gugeler, Wolfgang Frey, Anna Zens, Johannes Kastner, Thomas Sottmann, Sabine Laschat
Summary: In Rh-catalyzed reactions using microemulsions, the chiral complex Rh(OAc) showed the greatest dependence on the composition of the microemulsion, indicating that the microenvironment significantly influences its catalytic activity and selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yannick Stoeckl, Thomas Fellmeth, Florian Bauer, Bianca Wank, Wolfgang Frey, Birgit Claasen, Anna Zens, Andreas Koehn, Sabine Laschat
Summary: Chiral trans-hydrindanes are important building blocks of polycyclic natural products. The scope and limitation of [4+2] cycloadditions of tetrahydroindanones with various dienes were studied. Acid-catalysis and thermal conditions lead to the formation of diastereomers with opposite stereoselectivity. Quantum-chemical computations revealed the reaction mechanism and control.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Marco Andre Grunwald, Alexander-Nicholas Egler-Kemmerer, Soeren Magnus Bauch, Max Ebert, Gabriele Braeuning, Anna Zens, Sabine Laschat
Summary: In this study, two series of dimers with different substituents were synthesized and their mesomorphic properties were investigated using various techniques. The results showed that the substituents and spacer lengths had a significant impact on the phase behavior. A packing model for the SmA phases was proposed based on the experimentally determined layer thickness. The findings provide insights into the influence of different substituents on the stability of liquid crystal phases.
Review
Chemistry, Multidisciplinary
Nadia Kapernaum, Alyna Lange, Max Ebert, Marco A. Grunwald, Christian Haege, Sebastian Marino, Anna Zens, Andreas Taubert, Frank Giesselmann, Sabine Laschat
Summary: Ionic liquid crystals (ILCs) have attracted significant attention due to their mesomorphic, liquid crystalline, and anisotropic properties. Recent research focuses on fundamental aspects, synthesis variations, and tuning of mesomorphic behavior of ILCs. Challenges ahead include commercialization and overcoming technical obstacles in the field.
Article
Chemistry, Physical
Julius A. Knoller, Robert Forschner, Wolfgang Frey, Johannes Lang, Angelika Baro, Anna Zens, Yann Molard, Frank Giesselmann, Birgit Claasen, Sabine Laschat
Summary: By synthesizing flavylium triflates with different thioether substitutions, the effects of thioethers on self-assembly and electronic properties were investigated. Experimental results showed that thioether substitutions on the B ring altered the linear optical properties in solution.
Article
Chemistry, Physical
Mohamed A. Kolmangadi, Glen J. Smales, Li ZhuoQing, Arda Yildirim, Eugen Wuckert, Sandy Eutionnat, Felix Demel, Patrick Huber, Sabine Laschat, Andreas Schoenhals
Summary: This study investigates the molecular mobility and electrical conductivity of a series of linear shaped columnar ionic liquid crystals with varying alkyl chain lengths. The results show that both the dynamics and electric conductivity of the system are influenced by the chain length. The study provides insights into the relationship between molecular structure and electrical properties.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
