Article
Multidisciplinary Sciences
Zitong Wu, Wenji Wang, Haodong Guo, Guorui Gao, Haizhou Huang, Mingxin Chang
Summary: Direct asymmetric reductive amination is an efficient method for obtaining chiral amines. In this study, the authors demonstrate how primary alkyl amines can undergo this transformation in the presence of an iridium catalyst with sterically tuneable chiral phosphoramidite ligands, leading to the synthesis of pharmaceutical compounds.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Rita Lopes, Alvaro Raya-Baron, M. Paula Robalo, Carolina Vinagreiro, Sonia Barroso, Maria J. Romao, Ignacio Fernandez, Mariette M. Pereira, Beatriz Royo
Summary: Two piano-stool iron(II) complexes with N-heterocyclic carbene ligands were synthesized and studied for their catalytic activity in the transfer hydrogenation of ketones. Complex 3 exhibited the highest catalytic activity among the series, with a TOF(50) value of 533 h(-1). A new species 3' containing a deprotonated amidate moiety was identified through NMR monitoring, and a green protocol for ketone reduction using glycerol as a hydrogen source and microwave irradiation with catalytic amounts of complex 3 and base was developed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
J. I. Badillo-Gomez, E. P. Sanchez-Rodriguez, R. A. Toscano, M. Gouygou, M. C. Ortega-Alfaro, J. G. Lopez-Cortes
Summary: A new phosphine-free [N,N,O]-tridentate Schiff base ligand L1 was synthesized using 2-Ferrocenyl-2-thiazoline as scaffold. The ligand was successfully obtained with an overall yield of 83% after two-step synthesis. L1 showed good coordination ability towards Ru(II) and exhibited moderate to excellent catalytic performance in transfer hydrogenation of various substrates.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yulin Sun, Zhuoyuan Liu, Donghan Liu, Mingshuai Zhang, Longkun Chen, Zhangmengjie Chai, Xue-Bing Chen, Fuchao Yu
Summary: Highly functionalized 4-alkylated 1,4-dihydropyridines (1,4-DHPs) are synthesized for the first time from cyclic ethers and enaminones via iron(II)-mediated oxidative free radical cascade C(sp(3))-H bond functionalization/C(sp(3))-O bond cleavage/cyclization reaction. This novel synthetic strategy provides an alternative method for the construction of 1,4-DHPs using esters as the C4 sources, and expands the application of ethers in heterocycle synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ishani Borthakur, Sameer Srivastava, Saloni Kumari, Sabuj Kundu
Summary: This paper reports for the first time an Ir-catalyzed tandem synthesis of various N-methylated tertiary amines through a three-component coupling of carbonyl compounds, amines, and methanol followed by reductive amination/N-methylation. The method demonstrates a wide range of substrate tolerance towards different functional groups and can be applied to the synthesis of pharmaceutically important drug molecules containing N-methyl groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xintuo Yang, Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. The (EtO)(2)MeSiH/BQ redox system is crucial for the highly selective and efficient hydrooxygenation, where alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides an efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Tingjie You, Maosheng Zhang, Jianhui Chen, Hongmei Liu, Yuanzhi Xia
Summary: A convenient method for the reductive cleavage of N-O bonds was described using a commercially available ruthenium(II) catalyst and a mixture of HCOOH/NEt3 as the hydride source under an air atmosphere. This catalytic system was applicable for a variety of N-oxygen-substituted amides, efficiently delivering the corresponding products with good functional group tolerance in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Lan Mei, Min Du, Yuan Zhang, Cheng Hou
Summary: This study investigates the mechanistic preference of a ruthenium complex with dual proton-responsive sites in borrowing-hydrogen N-alkylation catalysis using DFT calculations. The results suggest that the gamma-NH site facilitates the rate-determining step via non-covalent interaction, while the alpha-NH site requires overcoming a higher activation energy barrier.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Danielle L. J. Pinheiro, Martin Nielsen
Summary: The chemoselective reduction of enamides to alpha-amino acids using Ru pincer complexes as catalysts and iPrOH and EtOH as H-donors and solvents is demonstrated. A range of alpha-amino acids is synthesized with good to excellent yields. Applications, large-scale synthesis, and a one-pot experiment are also reported. Deuterium-labeling experiments show high regioselectivity between the alpha- and beta-positions of the alkene unit.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Francisco D. Fagundes, Elthon F. Passos, Juliana P. da Silva, Marcio P. de Araujo
Summary: The complexes trans/cis-[RuCl2(DPEphos)(ampy)] (1a, 1b) and trans/cis-[RuCl2(DPEphos)(en)] (2a, 2b) were synthesized from the reactions of mer-[RuCl2(DPEphos)(PPh3)] with the corresponding amine. Isomer 1a was observed in situ at room temperature, while 1b was obtained when the reaction was performed under reflux. Isomer 2a was obtained at room temperature, and 2b was observed under reflux or when a CH2Cl2 solution of 2a was exposed to light. Cyclic voltammetry studies showed reversible processes for 1b and 2a. Both 1b and 2a exhibited high conversions and TOF values as pre-catalysts for the reduction of acetophenone and p-substituted acetophenones.
JOURNAL OF COORDINATION CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Siyu Guo, Xiaohu Zhao, Yonggui Robin Chi
Summary: Nickel complexes ligated by strongly donating diphosphines catalyze enantioselective hydrogenation for the preparation of acyclic and cyclic beta-amido esters, with a combination of acetic acid and indium powder providing protons and electrons to form nickel hydrido complexes under umpolung hydrogenation conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Dawei Gong, Degong Kong, Yufei Li, Caiyu Gao, Lina Zhao
Summary: A nickel-catalyzed semihydrogenation of azoarenes to hydrazoarenes with NH3BH3 is developed, exhibiting good functional group tolerance and a high turnover frequency at room temperature. Control and deuterium-labeling experiments reveal that the ethanol hydroxyl and BH3 groups each donated one hydrogen, resulting in the formation of B-(OEt)(3) and H-2 as main byproducts. Density functional theory calculations suggest a ligand-to-ligand hydrogen transfer mechanism for the reaction. This study presents a novel nickel catalytic system for the semihydrogenation of azoarenes.
Article
Chemistry, Organic
Dawei Gong, Degong Kong, Na Xu, Yuhui Hua, Bo Liu, Zhanlin Xu
Summary: A new method for the synthesis of hydrazoarenes is developed by using ethanol as a hydrogen source and a bidentate Ru(II)-NC complex as the catalyst. The presence of a weak base is crucial for efficient semihydrogenation, which prevents hydrazoarene dehydrogenation under strongly basic conditions. Control experiments and density functional theory calculations confirm the mechanism as Meerwein-Ponndorf-Verley mechanism, with ethyl acetate as the only byproduct. This study offers a new and simple approach for the synthesis of hydrazoarenes.
Article
Chemistry, Organic
Song Feng, Baoqi Ren, Lige Li, Fengmin Xia, Zhiyong Tang, Yu Zhang, Xiaoning Liu, Qixuan Lu, Wenge Zhong
Summary: This method achieves the N-heteroaryl-directed Ru-catalyzed asymmetric hydrogenation of α,α-disubstituted vinyl ethers with good to excellent enantioselectivities, providing an attractive approach for synthesizing pharmaceutically active heteroaryl compounds containing chiral ether units.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yanping Xia, Sen Wang, Rui Miao, Jianhua Liao, Lu Ouyang, Renshi Luo
Summary: Cationic iridium complexes were demonstrated to catalyze the transfer hydrogenation of oximes, providing access to N-alkoxy amines and hydroxylamines. The reaction rate was accelerated by trifluoroacetic acid. The practical application of this method was demonstrated by the synthesis of a fungicide in high yields, and the asymmetric synthesis of chiral N-alkoxy amines showed potential for further development.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Pinkie Ntola, Holger B. Friedrich, Abdul S. Mahomed, Ezra J. Olivier, Alisa Govender, Sooboo Singh
Summary: This study presents the structural characterization of VOx/MgO powders prepared by a stoichiometric solution combustion synthesis using five different fuels. The synthesized powders were characterized using X-ray diffraction, Raman spectroscopy, Inductively Coupled Plasma Emission Spectroscopy, Scanning Electron Microscopy, and Aberration Corrected Transmission Electron Microscopy. The results showed that the selection of fuel influenced the microstructure, vanadate phase formation, and dispersion of each powder. By correlating experimental microstructural parameters with calculated thermodynamic parameters, the study demonstrates the crucial role of fuel in controlling reaction kinetics.
MATERIALS CHEMISTRY AND PHYSICS
(2022)
Article
Crystallography
Halliru Ibrahim, Sizwe J. Zamisa, Muhammad D. Bala, Holger B. Friedrich
Summary: This passage describes the crystal structure parameters and related numerical values of a molecule, including its lattice parameters, cell volume, space group, etc.
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-NEW CRYSTAL STRUCTURES
(2022)
Article
Chemistry, Multidisciplinary
Revana Chanerika, Mzamo L. Shozi, Holger B. Friedrich
Summary: In this study, catalysts with different silver loadings supported on alumina were prepared and characterized. It was found that the catalysts with different silver loadings had different sizes of metal nanoparticles. In the competitive hydrogenation reaction, nanoparticles with sizes of 10-15 nm showed high conversion and stable operation. The performance of the catalysts was influenced by both the metal and support, with the support playing an important role in the overall acidity of the catalysts.
Article
Crystallography
David O. Ywaya, Holger B. Friedrich, Muhammad D. Bala, Lynette Soobramoney, Halliru Ibrahim
Summary: This article describes the crystal structure of compound C19H27N5. The compound crystallizes in the orthorhombic Pbca (no. 61) space group with lattice parameters of a = 9.8515(12) angstrom, b = 16.508(2) angstrom, c = 29.817(3) angstrom. Important physical parameters such as V = 4849.3(10) angstrom^3, Z = 8, R-gt(F) = 0.0409, and wR(ref)(F-2) = 0.1082 are also provided.
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-NEW CRYSTAL STRUCTURES
(2022)
Article
Chemistry, Physical
Revana Chanerika, Mzamo L. Shozi, Mirko Prato, Holger B. Friedrich
Summary: Selective hydrogenation of 1-octyne to 1-octene was achieved using a 5Ag catalyst coated with various ionic liquids. The addition of different ionic liquids improved the selectivity to 1-octene, although the catalyst stability remained a challenge.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Dunesha Naicker, Saba Alapour, Sizwe J. Zamisa, Holger B. Friedrich
Summary: In this study, three ruthenium complexes were synthesized and characterized for the oxidation reactions of n-octane and styrene with different hybridizations of CH bonds. Ru-oxo species were found to act as active catalysts in the reactions, but exhibited different catalytic behaviors in the chosen models. These complexes are promising candidates for catalyzing C-1 partial oxidation and producing octanal and 1-octanol with high selectivity, which are in high demand in the industry.
JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Physical
Aaron L. Folkard, Majid D. Farahani, Abdul S. Mahomed, Holger B. Friedrich
Summary: Selective hydrogenolysis of glycerol to propanol is a sustainable reaction with great market potential. This study explores the use of Cu-HSiW catalysts for this reaction and achieves a high yield through advanced characterization techniques. The modification of the catalyst improves its performance and lifetime.
Review
Chemistry, Inorganic & Nuclear
Halliru Ibrahim, Muhammad D. Bala, Holger B. Friedrich
Summary: This review elaborates on the chronological development of imino-NHC ligands and their complexes with late first-row transition metals utilized in homogeneous catalysis. Imino-NHC ligands have gained popularity due to their general stability, better resistance to degradation, and suitable coordinative and electronic properties for various catalytic transformations.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Physical
Sanele Moloi, Majid D. Farahani, Abdul S. Mahomed, Sooboo Singh, Holger B. Friedrich
Summary: VO2/TiO2 is a widely used material in various catalytic reactions, showing promising activity for CO2-assisted dehydrogenation of alkanes. The dispersion of V3+ on TiO2 with nanorod morphology resulted in a catalyst with monomeric VOx species, which exhibited good activity. The detailed characterization data provided in this study contribute to understanding these materials.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Physical
Revana Chanerika, Mzamo L. Shozi, Mirko Prato, Holger B. Friedrich
Summary: This study investigated the selective hydrogenation of a mixed 1-octyne/1-octene feed using solid catalysts with an ionic liquid layer (SCILLs). Results showed that coating the catalysts with an ionic liquid layer increased the yield of 1-octene and maintained stability during the experiments.
Article
Chemistry, Physical
Victor O. Anyanwu, Holger B. Friedrich, Abdul S. Mahomed, Sooboo Singh, Thomas Moyo
Summary: Cubic and rhombohedral phases of lanthanum manganite were synthesized using a high-pressure reactor. The synthesized LaMnO3, validated through X-ray diffraction, exhibited significant structural transformation from the cubic to the rhombohedral phase, resulting in changes in unit cell volumes. Transmission electron microscopy analysis confirmed small particle sizes, no agglomeration, and good crystallinity. The material's particle characteristics, high purity, and high surface area make it suitable for important technological applications, including the synthesis of perovskite oxides.
Article
Multidisciplinary Sciences
Majid D. Farahani, Cheslin Moodley, Abdul S. Mahomed, Holger B. Friedrich
Summary: In this study, a Pt-V/CeO2 catalyst was developed for amide hydrogenation under mild conditions. It was found that oxygen vacancies on the ceria surface play a crucial role in the catalytic activity, with the absence of oxygen vacancies enhancing the hydrogenation ability of Pt sites and promoting the in situ formation of oxophilic V3+.
Article
Chemistry, Physical
Revana Chanerika, Mzamo L. Shozi, Mirko Prato, Holger B. Friedrich
Summary: The effect of tetrabutylammonium nitrate as a surface coating over 1Pd9Ag/Al2O3 in the selective hydrogenation of 1,7-octadiene was studied. The results showed that the coating significantly decreased the conversion and selectivity of 1-octene. However, no net gain in 1-octene was observed. The thickness of the coating also affected the conversion and selectivity, with a thicker coating leading to further decline. Characterization of the catalysts confirmed leaching of the ionic liquid and re-establishment of the metal-support interaction.
Article
Chemistry, Physical
Lindokuhle B. Ngema, Majid D. Farahani, Shaine Raseale, Nico Fischer, Abdul S. Mohamed, Sooboo Singh, Holger B. Friedrich
Summary: Employing a reduction-oxidation pretreatment successfully modified the Co3O4 | ZrO2 catalyst surface, leading to improved CO oxidation activity. The restructuring of Co3O4 to CoO species on the ZrO2 surface formed a highly active Co3O4-CoO | ZrO2 interface, resulting in enhanced CO2 desorption sites and CO oxidation activity. The findings highlight the importance of surface modification for improving CO preferential oxidation activity.
SURFACES AND INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Mzamo L. Shozi, Xolelwa Zulu, Holger B. Friedrich
Summary: A series of phosphorus and nitrogen-based ethylene oligomerization ligands were reported, characterized, and tested for activity and selectivity towards 1-octene. The supported catalysts showed comparable activity to their homogeneous counterparts, with high selectivities to 1-octene in the C8 products.
SOUTH AFRICAN JOURNAL OF CHEMISTRY-SUID-AFRIKAANSE TYDSKRIF VIR CHEMIE
(2022)