Article
Chemistry, Physical
Chiara Palladino, Tommaso Fantoni, Lucia Ferrazzano, Beatrice Muzzi, Antonio Ricci, Alessandra Tolomelli, Walter Cabri
Summary: The copper-free Heck-Cassar-Sonogashira (HCS) reaction is a powerful method for C-C bond formation in organic synthesis and has several industrial applications. This study investigated the mechanism of the copper-free HCS reaction by conducting stoichiometric and catalytic reactions and analyzing the role of the base. The results showed that the base can accelerate the reduction of the precatalyst and decrease the energy barrier for the alkyne carbopalladation step.
Article
Chemistry, Applied
Ahmed R. Abdellah, Abu-Bakr AAM. El-Adasy, Ahmed A. Atalla, Kamal I. Aly, Hani Nasser Abdelhamid
Summary: In this study, COFs synthesized via the solvothermal method were used as supports for in-situ growth of Pd NCs, resulting in catalysts with small particle sizes. The materials were characterized using various techniques, and the Pd NCs@COFs exhibited excellent catalytic performance and stability in C-C formation reactions.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Chemistry, Physical
Victoria Dimakos, Daniel P. Canterbury, Sebastien Monfette, Philipp C. Roosen, Stephen G. Newman
Summary: This study describes a Pd-catalyzed method for the direct and selective alpha-arylation of cyclic enones using (hetero)aryl triflates. Optimized ligands and additives were employed to achieve high selectivity. Preliminary mechanistic investigations suggest that the reaction proceeds through enone activation and Pd-catalyzed enolate arylation, resembling a Morita-Baylis-Hillman reaction.
Editorial Material
Chemistry, Physical
Valentine P. Ananikov
Summary: Methods for direct one-step replacement of a hydrogen atom in a C-H bond by an organic functional group can create enormous possibilities for synthetic applications. The discovery of the reaction of organopalladium complexes with olefins has opened a new era in catalysis and organic chemistry.
Article
Materials Science, Paper & Wood
Melike Caliskan, Talat Baran
Summary: A novel nanocatalyst system (Pd@CS-ZnO) was developed by attaching palladium nanoparticles onto a hybrid nanocomposite of chitosan and ZnO nanoparticles. The catalytic efficiency of Pd@CS-ZnO was assessed for Heck coupling reaction, showing promising results. The Pd@CS-ZnO nanocatalyst demonstrated easy separation and high chemical stability, making it a cost-effective and eco-friendly catalyst system.
Article
Biochemistry & Molecular Biology
Guanying Shi, Zhenhua Dong
Summary: A hybrid catalyst, Pd@AEPOP, immobilized on an amide and ether functionalized porous organic polymer, has been reported to be an effective heterogeneous catalyst for the synthesis of diphenylethene derivatives via the Heck cross-coupling reaction of aryl iodides with styrene. Excellent yields can be achieved using a 0.8 mol% Pd catalyst loading under optimized reaction conditions. The Pd@AEPOP catalyst can also be applied for the Suzuki reaction and nitroarene reduction.
Article
Chemistry, Multidisciplinary
Aurelien Adenot, Lucile Anthore-Dalion, Emmanuel Nicolas, Jean-Claude Berthet, Pierre Thuery, Thibault Cantat
Summary: A new air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction for the synthesis of diaryl sulfones has been developed, tolerating a wide range of polar functional groups. Control experiments and DFT calculations elucidated the mechanism involving the formation of a Cu(I)-sulfinate intermediate through fast insertion of a SO2 molecule.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Sangeth Jenthra, Totan Mondal, Gregor Kemper, Marcus Lantzius-Beninga, Markus Hoelscher, Walter Leitner
Summary: A highly chemo- and regioselective decarboxylative Heck-type coupling of carboxylic acids and terminal olefins was achieved using a catalytic system composed of Pd(OAc)(2) in the presence of phosphine-sulfonamido ligands. The bulky ligand L1 favored the formation of 1,1-disubstituted branched olefins with high selectivity, while the less bulky ligand L2 resulted in the formation of 1,2-disubstituted linear products in high yield. Detailed mechanistic investigation revealed that the aryl substituent at the sulfonamide group of ligand L1 favored 1,2-insertion, while the less bulky ligand L2 favored 2,1-insertion.
Article
Chemistry, Physical
Elizaveta V. Larina, Anna A. Kurokhtina, Elena V. Vidyaeva, Nadezhda A. Lagoda, Alexander F. Schmidt
Summary: The study focused on the role of ionic Pd species in catalytic systems for cross-coupling reactions, specifically investigating the differential selectivity of the Mizoroki-Heck reaction with competition between aryl halides or alkenes. It was found that the additives of tertiary phosphine and halide salts significantly affect the catalytic activity of anionic Pd complexes, determining the regioselectivity of the reaction.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fariba Jafari, Arash Ghorbani-Choghamarani, Neda Hasanzadeh
Summary: Boehmite nanoparticles were synthesized in aqueous solution by combining Al(NO3)3·9H2O and NaOH, which were then converted to Pd-Gu@BOEH nanocatalyst for chemoselective C-C bond formation reactions. The catalyst and products were characterized, and the recycled catalyst exhibited good stability during reaction processes.
RESEARCH ON CHEMICAL INTERMEDIATES
(2021)
Article
Chemistry, Multidisciplinary
Jun Li, Gaoliang Wang, Honglei Yuan, Kun Feng, Xianke Sun
Summary: A Schiff-based Pd(0) nanocatalyst was successfully developed by modifying silica gel and exhibited efficient catalytic activity in Mizoroki-Heck and Suzuki-Miyaura coupling reactions. The catalyst could be reused multiple times without significant loss of activity.
ARABIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Siou-Wei Liang, Yingjie Guo, Wan-Ching Lee, Pin-Rui Zeng, Tzu-Hao Lin, Pei-Zhen Xie, Hsuan-Hao Kang, I-Chung Lu, Yu-Chang Chang
Summary: Two newly designed Pd(II) precatalysts were synthesized and used to efficiently convert unreactive aryl chlorides, benzyl chlorides, and benzoyl chlorides. The deprotonation of the precatalysts led to the dissociation of NHC, and the proposed Pd(II) species could be reduced to Pd(0) using ethoxide. The size of salt additive cations and the basicity of the base were found to influence the catalytic properties.
Article
Chemistry, Inorganic & Nuclear
Norul Azilah Abdul Rahman, Najwa Asilah M. Shamsuddin, Mazni Musa, Yatimah Alias, Idris Sharif, Ahmad Husaini Mohamed, Karimah Kassim, Nur Rahimah Said
Summary: This study developed a PVA-SA-PdCl2 catalyst using an ultrasonic-assisted method, which exhibited excellent recyclability and reproducibility. The catalytic reaction achieved a 100% conversion rate when employing a 1 mmol% catalyst load, K2CO3 base, DMA solvent, and a 60 min reaction at 165 degrees C.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Chengwei Liu, Michal Szostak
Summary: Decarbonylative Sonogashira cross-coupling of carboxylic acids by palladium catalysis involves in situ activation of carboxylic acids to form aryl-Pd intermediate, followed by coupling with alkynes to generate new C(sp(2))-C(sp) bonds efficiently. This methodology can be applied to the derivatization of pharmaceuticals and mechanistic studies suggest the decarbonylation precedes transmetalation in this process.
Article
Chemistry, Multidisciplinary
Rajesh Kancherla, Krishnamoorthy Muralirajan, Sayan Dutta, Kuntal Pal, Bo Li, Bholanath Maity, Luigi Cavallo, Magnus Rueping
Summary: The development of metal complexes that can function as both photocatalysts and cross-coupling catalysts is challenging. This study reports that divalent palladium can act as a light-absorbing species to achieve carbon-nitrogen cross-coupling reactions under air. Palladium acetate can be used as both the photocatalyst and cross-coupling catalyst for the selective cross-coupling amination of differently substituted aryl halides at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Giulia Giubertoni, Gijs Rombouts, Federico Caporaletti, Antoine Deblais, Rianne van Diest, Joost N. H. Reek, Daniel Bonn, Sander Woutersen
Summary: Inspired by NMR, IR-DOSY is a technique that characterizes both molecular structure and size using infrared spectroscopy. It achieves sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration. Molecules with different sizes are separated into distinct sets of IR peaks in the IR-DOSY spectrum. The 3D-IR-DOSY combines conformation sensitivity with size sensitivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
T. Bouwens, T. M. A. Bakker, K. Zhu, J. Hasenack, M. Dieperink, A. M. Brouwer, A. Huijser, S. Mathew, J. N. H. Reek
Summary: Inspired by natural photosynthesis, we use supramolecular machinery to inhibit electron-hole recombination in molecular photoelectrochemical devices, resulting in an increase in power conversion efficiency.
Article
Chemistry, Physical
Martin D. Witte, Sebastian B. Beil, Adriaan J. Minnaard, Marios Kidonakis, Augustin Villotet
Summary: Quinuclidine-mediated electrochemical oxidation provides a versatile and selective method for synthesizing C3-ketosaccharides with high yields, which is complementary to Pd-catalyzed or photochemical oxidation and different from the electrochemical oxidation of methylene and methine groups as it does not require oxygen.
Article
Chemistry, Multidisciplinary
Johannes G. de Vries
Summary: This article reviews various processes for converting lignocellulose or sugars into useful chemicals. Catalytic pyrolysis of lignocellulose produces hydrocarbon mixtures rich in alkenes or aromatics. These processes can also be applied to plastic waste or mixtures of biomass and plastic waste. New applications of furfural are emerging, and the production of furfural derivatives, such as 2-methyltetrahydrofuran, is increasing. The production of levulinic acid and its derivatives is about to be scaled up. Additionally, there are several processes in development for the production of glycols from glucose or bioethanol, and a plant for converting bioethanol into butadiene is currently under construction in Poland.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Katharina Konieczny, Felix J. de Zwart, Eduard. O. Bobylev, Eszter Barath, Sergey Tin, Bernd H. Mueller, Joost N. H. Reek, Bas de Bruin, Johannes G. de Vries
Summary: Researchers achieved enantioselective hydrogenation of cyclic enamides using an earth-abundant cobalt-bisphosphine catalyst. The catalytic system, CoCl2/(S,S)-Ph-BPE, reduced trisubstituted carbocyclic enamides to saturated amides with high activity and excellent enantioselectivity (up to 99%). The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations suggested a sigma-bond-metathesis pathway for the hydrogenation of the carbon-carbon double bond, involving a high spin cobalt (II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Catriona C. James, Bas de Bruin, Joost N. H. Reek
Summary: The importance of transition metal catalysis lies in its wide range of applications, including the synthesis of chemicals, natural products, and pharmaceuticals. However, a relatively new application is the catalysis of new-to-nature reactions inside living cells. The complex environment of living cells poses challenges to transition metal catalysts due to the potential inhibition or deactivation by various biological components. In this review, we summarize the current progress in the field of transition metal catalysis, focusing on the evaluation of catalysis efficiency under living cell and biological conditions. Catalyst poisoning is a common issue in this field, and we suggest that future research should explore physical and kinetic protection strategies to enhance the reactivity of catalysts in cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Eduard O. O. Bobylev, Julian Ruijter, David A. I. I. I. A. Poole, Simon Mathew, Bas de Bruin, Joost N. H. Reek
Summary: Inspired by catalytic regulation in living cells, we developed a Pt2L4 cage whose activity can be controlled by binding effector molecules. The cage shows catalytic activity in the lactonization reaction, with the rate depending on the bound effector guest. Some effector guests enhance the rate by up to 19-fold, while one decreases it by 5-fold. When specific substrate mixtures are used, both starting materials and products act as guests, enhancing catalytic activity for one substrate and reducing it for the other. The addition of effector molecules enables the development of more complex, metabolic-like catalyst systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Catriona C. James, Petrus C. M. Laan, Bas de Bruin, Joost N. H. Reek
Summary: Olefin metathesis catalysts, such as AquaMet, are susceptible to decomposition under biologically relevant conditions. Current stabilizing strategies have limited applicability under these conditions. Encapsulation of AquaMet within a supramolecular metallocage, with nitrate counterions, enhances the catalyst activity. Replacement of AquaMet's chloride ligands with nitrates through simple anion-exchange leads to higher yields of ring-closed product under aqueous and biological conditions. This kinetic protection strategy of transition metal catalysts may find applications in other in vivo catalytic reactions.
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Shasha Zheng, Fabian Kallmeier, Eszter Barath, Sergey Tin, Johannes G. de Vries
Summary: A readily available chiral Ru/bisphosphine catalyst was used to achieve the direct asymmetric reductive amination of bio-based levulinic acid (LA) to produce enantioenriched 5-methylpyrrolidinone with excellent enantioselectivity (up to 96% ee) and high isolated yield (up to 89%). Methyl levulinate (ML), a byproduct from the industrial production of 2,5-furandicarboxylic acid (FDCA), can be used as a substitute for LA with similar reactivity and selectivity. Mass spectrometry and isotope labelling studies suggest that the chiral lactam is formed through imine-enamine tautomerization/cyclization followed by asymmetric hydrogenation of the cyclic enamide.
Article
Chemistry, Inorganic & Nuclear
David A. Poole III, Eduard O. Bobylev, Bas de Bruin, Simon Mathew, Joost N. H. Reek
Summary: This article investigates the self-assembly of spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands. The self-assembly process is found to be sensitive to the solvents, reagents, and/or reactants used, which hinders the development of desired palladium-based cages. The study reveals that ligand substitution can be facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Petrus C. M. Laan, Eduard O. Bobylev, Felix J. de Zwart, Joppe A. Vleer, Alessandro Troglia, Roland Bliem, Gadi Rothenberg, Joost N. H. Reek, Ning Yan
Summary: Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a difficult task, but immobilizing supramolecular cages to control the ligand design of the primary- and secondary coordination spheres allows for fine-tuning of catalytic properties. The study of the hydrolysis of ammonia borane revealed that placing a well-defined reaction pocket around the active site can enhance catalytic performance, resulting in diffusion-controlled reaction kinetics.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Kyzgaldak Ramazanova, Soumyadeep Chakrabortty, Fabian Kallmeier, Nadja Kretzschmar, Sergey Tin, Peter Loennecke, Johannes G. de Vries, Evamarie Hey-Hawkins
Summary: Sulfur-protected enantiopure P-chiral 1-phosphanorbornane silyl ethers 5a,b were obtained in high yields via reaction with tert-butyldimethylsilyl chloride (TBDMSCl) and triphenylsilyl chloride (TPSCl), and were subsequently purified and characterized. The bulky monodentate enantiopure phosphorus(III) 1-phosphanorbornane silyl ethers 6a,b were obtained by desulfurization with excess Raney nickel, and showed better activity and selectivity as ligands in iridium-catalyzed asymmetric hydrogenation.
Article
Chemistry, Multidisciplinary
Shigenari Ishizuka, J. Hessel M. van Dijk, Tomomi Kawakita, Yuji Miyamoto, Yumi Maeda, Masamichi Goto, Guillaume Le Calvez, L. Melanie Groot, Martin D. Witte, Adriaan J. Minnaard, Gijsbert A. van der Marel, Manabu Ato, Masamichi Nagae, Jeroen D. C. Codee, Sho Yamasaki
Summary: Although leprosy is an ancient disease, the mechanism of pathogenicity of Mycobacterium leprae is not fully understood. In this study, the researchers identified phenolic glycolipid-III (PGL-III) as a specific ligand for the immune receptor Mincle. PGL-III was found to be a more potent ligand than trehalose dimycolate, a well-known ligand from Mycobacterium tuberculosis. The study also revealed the unique recognition mode of Mincle and its interaction with multiple Mincle molecules. The findings suggest that PGL-III triggers protective immunity against M. leprae.
ACS CENTRAL SCIENCE
(2023)
Article
Green & Sustainable Science & Technology
Shasha Zheng, Zhihong Wei, Bartosz Wozniak, Fabian Kallmeier, Eszter Barath, Haijun Jiao, Sergey Tin, Johannes G. de Vries
Summary: This article introduces a strategy for synthesizing benzenoid aromatics from bio-based feedstock, which shows the potential to replace fossil-based resources in aromatics production.
NATURE SUSTAINABILITY
(2023)
Article
Chemistry, Organic
Niels R. M. Reintjens, Martin D. Witte, Adriaan J. Minnaard
Summary: Thioglycosides or S-linked-glycosides are important glycomimetics that can be synthesized by glycosylating deoxythio sugar acceptors. A carbonyl group formed by site-selective oxidation of unprotected saccharides can be converted into a thiol moiety, allowing for the preparation of deoxythio sugars through S(N)1 substitution reactions. The combination of these deoxythio sugars with protecting group-free glycosylation of glycosyl fluorides enables a protecting group-free synthesis of thioglycosides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)