Review
Chemistry, Multidisciplinary
Massimo C. D'Alterio, Eric Casals-Cruanas, Nikolaos V. Tzouras, Giovanni Talarico, Steven P. Nolan, Albert Poater
Summary: The story of C-C bond formation involves various reactions, with Suzuki-Miyaura reaction being one of the most outstanding ones. The focus is on the formation of catalytically active species, with preactivation potentially playing a role as the rate determining step in the overall reaction. Computational chemistry plays a key role in identifying the rate determining step and achieving milder conditions in experimental settings through predictive catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jie Zhang, Yaning Wang, Chang You, Mingying Shi, Xueling Mi, Sanzhong Luo
Summary: We report a synergetic chiral primary amine and rhodium catalysis for the asymmetric coupling of beta-ketocarbonyls and alkynes. This method enables the synthesis of linear allylation products with all-carbon quaternary centers in high regio- and enantioselectivities.
Article
Multidisciplinary Sciences
Haigen Fu, Jingzhe Cao, Tianzhang Qiao, Yuyin Qi, Simon J. Charnock, Samuel Garfinkle, Todd K. Hyster
Summary: This study reports a highly chemoselective and enantioselective Csp(3)-Csp(3) XEC reaction catalyzed by flavin-dependent 'ene'-reductases (EREDs). The photoexcitation of the enzyme-templated charge-transfer complex enables the chemoselective reduction of alkyl halides and high enantioselectivity.
Article
Biochemistry & Molecular Biology
J. Alkabli, Moustafa A. Rizk, Reda F. M. Elshaarawy, W. N. El-Sayed
Summary: The newly developed IVCSSB scaffold effectively supports Pd(II) and Ru(II) ions in Suzuki coupling reactions, exhibiting excellent catalytic activity and stability. Pd(II)IVCSSB1 maintains its catalytic activity even after five consecutive operation runs and shows excellent selectivity towards cross-coupling reactions.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2021)
Article
Chemistry, Organic
Huicong Xing, Meijuan Chen, Dong Zhang, Zhishuai Geng, Peizhong Xie, Teck-Peng Loh
Summary: A transition-metal-free catalytic system was developed for the dehydrative cross-coupling of unactivated primary/secondary alcohols with amines/amides, achieving the cleavage of C-OH bond and formation of C-N bond under environmentally benign conditions.
Article
Chemistry, Physical
Lukas Hoff, Gleb A. Chesnokov, Anthony Linden, Karl Gademann
Summary: This study presents a thorough mechanistic investigation of the Pd-catalyzed and Ag-mediated cross-coupling reaction between monosubstituted tetrazine and boronic acids. Through kinetic analyses, isolation of intermediates, and computational methods, insights into the mechanism were obtained. The study also demonstrated the experimental confirmation of a highly electron-deficient ligand and the impact of mechanistic understanding on the generality of the reaction scope through a data-driven workflow.
Article
Chemistry, Physical
Antonio J. LaPorte, Yao Shi, Jason E. Hein, Martin D. Burke
Summary: Stereospecific Csp(3) Suzuki-Miyaura cross-coupling simplifies the synthesis of stereochemically complex small molecules, but current methods are not compatible with complex building blocks commonly found in natural products and other complex targets. This study presents a method for embedding the alpha-methyl-beta-hydroxyl motif within stereochemically defined secondary alkyl boronic ester building blocks, allowing for stereospecific cross-coupling. The use of beta-aryloxysilyl groups addresses the decrease in reactivity and side reactions associated with beta-oxygen-containing Csp(3) boronic esters. Mechanistic studies reveal the activation of a dihydroxysiloxaborolate as a transmetalation partner in a stereospecific process that retains configuration.
Article
Chemistry, Multidisciplinary
Ketan Kumar, Prashant Kumar, Bara Singh, Sonu Yadav, Uttam K. Mishra, Arshad J. Ansari, S. S. Ramasastry
Summary: The catalysis by transition metals is a powerful tool to access molecules with broad structural and functional diversity. Recent literature has shown the tremendous potential of transition metal-catalyzed processes in advancing organic synthesis. New conceptual advancements in palladium-catalyzed Alder-ene type cycloisomerization reactions, C-H functionalizations, and one-pot multicatalytic processes have become essential tools to access new classes of molecules.
Article
Chemistry, Multidisciplinary
Joshua D. Sieber, Raphael K. Klake, Toolika Agrawal, Dang Binh Ho, Samantha L. Gargaro, Stephen Collins, Mytia D. Edwards
Summary: This study describes Pd-catalyzed allylic alkylation of C-based nucleophiles using both chiral and achiral allenamides, resulting in high yields of synthetically valuable (E)-enamide products with high E:Z selectivity and generating a quaternary carbon atom. The study also highlights some potential stereocontrolled applications of the resultant (E)-enamide functionality.
ISRAEL JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Multidisciplinary
Zhong-Sheng Nong, Xin-Ran Chen, Pu-Sheng Wang, Xin Hong, Liu-Zhu Gong
Summary: This study reports a new catalytic reaction that converts chiral substrates into enantiomerically enriched products. Through mechanistic investigations, a new catalyst activation pool was discovered and demonstrated to possess high selectivity and conversion rates. This research provides new insights for developing highly selective catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Weixu Lu, Xiaoqiang Yu, Ming Bao
Summary: In this paper, a group of copper-based ternary deep eutectic solvents (Cu-DESs) were synthesized and applied in Glaser-type homo- and cross-coupling of terminal alkynes. These reactions occurred under exogenous-ligand-free, base-free, and additive-free conditions, providing satisfactory to excellent yields (up to 99%) under mild conditions. The Cu-DESs can be recycled eight times, with water being the only by-product, complying fully with the principles of green chemistry.
Article
Biochemistry & Molecular Biology
Xinjuan Li, Zhangquan Zhou, Yanan Wang, Jiaxin Dong, Xianbin Jia, Zhiguo Hu, Qingcong Wei, Weiwei Zhang, Yuqin Jiang, Jiaojiao Zhang, Yahao Dong
Summary: Starch-SB serves as a supporting material for palladium stabilization, resulting in a new air and moisture-stable palladium composite (Starch-SB-Pd(II)). This composite shows high activity and stability in Suzuki cross-coupling reactions due to the cooperative interactions between multifunctional capturing sites on starch and palladium species. The experiments also demonstrate the recyclability of this starch-supported catalytic system.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2023)
Review
Chemistry, Multidisciplinary
Fatemeh Mohajer, Majid M. Heravi, Vahideh Zadsirjan, Nargess Poormohammad
Summary: The Sonogashira reaction is a key cross-coupling reaction in organic synthesis, forming a C-C bond between a vinyl or aryl halide and a terminal alkyne. While traditionally requiring copper and phosphines or amines as co-catalysts and bases, recent developments have enabled the reaction to proceed without these components. This advancement could promote the principles of green chemistry and enhance the economic feasibility of the reaction.
Article
Materials Science, Paper & Wood
Mohamed Said El Ouahabi, Md Bin Yeamin, Raquel Rivas, Farid El Guemmout, Mar Reguero, Anna M. Masdeu-Bulto, Ali Aghmiz
Summary: Vegetal residues combined with nucleophiles can serve as catalysts for carbon dioxide fixation in epoxides to form cyclic carbonates, with the best performance seen in combinations of olive bones, grape waste, date pit, and corn leaves husk residues with tetrabutylammonium bromide. High conversions were achieved at low nucleophile loading under mild conditions. The vegetal wastes were stable under catalytic conditions and recyclable after suitable treatment.
Article
Crystallography
Siham Iksi, Farid El Guemmout, Mar Reguero, Anna M. Masdeu-Bulto, Ali Aghmiz
Summary: The structure of a Zn(II) complex with NN'O-donor ligand is described, showing a five-coordinate environment with a square-pyramidal distorted geometry. The experimental results show a good correlation with the calculated ones.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2021)
Review
Chemistry, Inorganic & Nuclear
Anna M. Masdeu-Bulto, Mar Reguero, Carmen Claver
Summary: Transformation of CO2 into consumer products is an alternative method to reduce global warming in addition to decreasing CO2 production. Photocatalytic route is an interesting way to convert CO2 into CO. Understanding the reaction mechanism is crucial for designing more efficient catalytic systems.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Green & Sustainable Science & Technology
Mar Reguero, Carmen Claver, Rui Miguel Barroso Carrilho, Anna Maria Masdeu-Bulto
Summary: This article reviews the recent research results of photocatalytic CO2 reduction using catalytic systems formed by molecular compounds anchored on solids.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Multidisciplinary Sciences
Martha Escarcega-Bobadilla, Mauricio Maldonado-Dominguez, Margarita Romero-Avila, Gustavo A. Zelada-Guillen
Summary: In the 1950s, Alan Turing demonstrated that coordinated reactions and diffusion can produce patterns without positional information, providing a chemical basis for morphogenesis. However, accessing these patterns using only one molecular component remains challenging.
Article
Chemistry, Physical
Alejandro Perez Alonso, Steven Mauries, Jean-Bernard Ledeuil, Lenaic Madec, Doan Pham Minh, Daniel Pla, Montserrat Gomez
Summary: In this study, nickel nanoparticles immobilized on halloysite-based supports were synthesized and the catalytic performance of these composite materials in hydrogenation reactions was evaluated. It was found that the NiNPs stabilized by quinidine on unfunctionalized halloysite (NiC) exhibited high catalytic activity and selectivity for a wide range of substrates.
Article
Chemistry, Multidisciplinary
Paulina Hernandez-Pacheco, Gustavo A. Zelada-Guillen, Margarita Romero-Avila, Roberto Carlos Canas-Alonso, Marcos Flores-Alamo, Martha Escarcega-Bobadilla
Summary: In this study, the synthesis and crystallographic characterization of a new Cu-Salphen compound and its use as a Lewis acid against guest anions were described. It was found that higher contents of Cu-Salphen resulted in larger and more homogeneous polymer sizes. The growth of the host's binding site was explained by factors such as polymer size, glass transitions, heat capacity, thermal degradation, guest-saturation degrees, and host-guest species distribution profiles. Spectrofluorimetry measurements showed that Cu-Salphen had larger blue-shifted luminescence in the polymers compared to the non-polymerized counterpart, and enhanced fluorescence upon guest association. A cooperative incorporation of the guests into the internally protected binding site pockets in the random coil polymer conformations was proposed.
Editorial Material
Chemistry, Multidisciplinary
Paulina Hernandez-Pacheco, Gustavo A. Zelada-Guillen, Margarita Romero-Avila, Roberto Carlos Canas-Alonso, Marcos Flores-Alamo, Martha V. Escarcega-Bobadilla
Summary: We synthesized and characterized a new Cu-Salphen compound, which acted as a Lewis acid to host guest anions in two different forms: a) free molecule, and b) copolymerized with protective co-monomers. Higher amounts of Cu-Salphen resulted in larger and more homogeneous polymer sizes. The polymer size, along with other factors such as glass transitions, heat capacity, thermal degradation, and host-guest species distribution, explained significant enhancements in the host's binding site.
Article
Chemistry, Physical
Alejandro Perez Alonso, Doan Pham Minh, Daniel Pla, Montserrat Gomez
Summary: An original bimetallic catalytic system based on Rh(I) and Co(0) in glycerol was developed for the efficient synthesis of biomass-derived amines through a tandem hydroaminomethylation reaction. The multicatalytic system demonstrated high chemoselectivity and good-to-excellent regioselectivity towards linear amines. Cobalt played a major role in reductive amination while rhodium was primarily responsible for hydroformylation.
Article
Biochemistry & Molecular Biology
Gustavo A. Zelada-Guillen, Jesus A. Rios-Arce, Mario A. Leyva-Peralta, Marcos Flores-Alamo, Juan Carlos Galvez-Ruiz, Kadiya Calderon, Martha V. Escarcega-Bobadilla
Summary: We synthesized and characterized organic Salphen compounds with bromine substituents at specific positions, both in symmetric and non-symmetric versions. The X-ray structure and full characterization of the new unsymmetrical varieties were described. For the first time, we found antiproliferative activity in metal-free brominated Salphen compounds tested on various cancer cell lines and a non-cancerous counterpart. Promising results were observed against prostate and colon adenocarcinoma cells, with selectivity up to 3-fold higher than the non-cancerous cells and 20-fold higher than doxorubicin controls.
CHEMISTRY & BIODIVERSITY
(2023)
Article
Chemistry, Multidisciplinary
Ekaterina Mamontova, Corine Trabbia, Isabelle Favier, Alejandro Serrano-Maldonado, Jean-Bernard Ledeuil, Lenaic Madec, Montserrat Gomez, Daniel Pla
Summary: In this study, small Ni-based nanoparticles supported on inorganic solid supports were prepared by decomposing organometallic precursors in refluxing ethanol under H-2 atmosphere. The prepared Ni-based nanocomposites showed high efficiency in the hydrogenation of unsaturated fatty acids under solvent-free conditions, with a high selectivity for the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the nanocomposites was highlighted.
Article
Chemistry, Physical
Nassima El Aouni, Claudia Lopez Redondo, Md Bin Yeamin, Ali Aghmiz, Mar Reguero, Anna M. Masdeu-Bulto
Summary: Zinc(II) complexes [Zn(L1-L5)Cl2] with tetra-aza donor ligands bearing phenanthroline and bipyridine bis(aniline) skeleton L1-L5 have been synthesized and characterized. The influence of three parameters, including steric hindrance of the orto substituent of aniline ring, central skeleton, and nature of non-aromatic amine, on the catalytic activity for CO2-cycloaddition to epoxides was analyzed using these ligands. X-ray diffraction characterization revealed that [Zn(L1)Cl2] and [Zn(L2)Cl2] are pentacoordinate, while [Zn(L5)Cl2] forms a four-coordinate tetrahedral complex. Computational calculations confirmed these results. When combined with tetrabutylammonium bromide (TBAB), these complexes exhibit high selectivity for the coupling of CO2 and terminal epoxides to form cyclic carbonates, with a TOF of up to 565 h-1.
MOLECULAR CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Garima Garg, Montserrat Gomez, Anna M. Masdeu-Bulto, Yaocihuatl Medina Gonzalez
Summary: This article discusses the importance and advantages of using compressed carbon dioxide (CO2) as a green solvent in designing eco-friendly chemical processes. It covers engineering fundamentals, catalyst design, and reaction conditions, emphasizing the specificity of CO2.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Nanoscience & Nanotechnology
Alejandro Serrano-Maldonado, Azzedine Bendounan, Mathieu G. Silly, Daniel Pla, Montserrat Gomez
Summary: Environmentally friendly catalytic composites based on cobalt and natural clay are used for selective hydrogenation of fatty acids and esters from agri-food industry wastes. Optimized conditions resulted in high conversions and chemoselectivity, producing saturated fatty acids or esters and tristearin as a food additive.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Paulina Hernandez-Pacheco, Gustavo A. Zelada-Guillen, Marcos Flores-Alamo, Martha Escarcega-Bobadilla
Summary: This study describes the synthesis, characterisation, and crystallographic analysis of a novel -OH functionalised Ni-Salphen complex and its hybrid nanomaterial counterparts in the form of the molecule covalently bonded to Edge-Oxidised Graphene Oxide. Spectrophotometric titrations and spectrofluorimetric emission profiles were used to investigate the association of the complex and nanomaterial with different pyridine-based guests. The results showed constant stoichiometry of association but different trends in association constants, which could be attributed to differences in the supramolecular environment at the binding site upon grafting and additional interactions arising from the graphene component.
SUPRAMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
