Article
Chemistry, Multidisciplinary
Hua-Hua Wang, Hui Shao, Guanglong Huang, Jianqiang Fan, Wai-Pong To, Li Dang, Yungen Liu, Chi-Ming Che
Summary: In this study, chiral iron porphyrin complexes were found to catalyze the asymmetric intramolecular C(sp(3))-H amination of aryl and arylsulfonyl azides, providing chiral indolines and benzofused cyclic sulfonamides, respectively. The reactions exhibited high enantioselectivity (up to 93% ee) and high yields (up to 99%) under mild conditions with 410 nm light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Matthew Edmondson, Eleanor S. Frampton, Chris J. Judd, Neil R. Champness, Robert G. Jones, Alex Saywell
Summary: A thermally induced order-disorder transition of 2H-TPP on Au(111) was investigated using scanning probe microscopy and X-ray photoelectron spectroscopy. The transition from an ordered close-packed phase to a disordered diffuse phase was found to be correlated with an on-surface cyclodehydrogenation reaction, and further heating of the diffuse phase resulted in the formation of a distinct nitrogen environment indicative of the Au-TPP species.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jian-Rong Dai, M. S. Jiang-Tao Sha, Min-Hua Zong, Ning Li
Summary: In this work, the horseradish peroxidase (HRP)-catalyzed aerobic oxidation of reduced nicotinamide cofactors (NADH) was reported. The oxidation was achieved at neutral and alkaline pH by using external amino acids (AAs). The presence of AAs promoted the formation of compound III and its decay back to the ground state. This method offers an alternative way to recycle NAD(P)(+) and has potential for HRP-catalyzed aerobic oxidations.
Article
Chemistry, Organic
Miyu Yokoyama, Yoshinori Okayasu, Yoichi Kobayashi, Hiroki Tanaka, Yohei Haketa, Hiromitsu Maeda
Summary: Dithienylnitrophenols were synthesized to form pi-electron anions, which were stabilized by intramolecular chalcogen bonding and combined with cations to form various ion pairs. The assembly modes of charge-by-charge in the solid state, along with stacking and photoinduced electron transfer behaviors in solution, were modulated by the different ionic species.
Review
Chemistry, Inorganic & Nuclear
Sam P. de Visser, Yen-Ting Lin, Hafiz Saqib Ali, Umesh Kumar Bagha, Gourab Mukherjee, Chivukula Sastri
Summary: This paper discusses the research progress on product selectivity in bioinorganic chemistry, focusing on the dominant role and mechanism of negative catalysis in enzymatic reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Review
Cell Biology
Amy E. Medlock, J. Catrice Hixon, Tawhid Bhuiyan, Paul A. Cobine
Summary: Metals are essential for human survival and development, but mishandling them can be toxic to cells. Mitochondrial metals play critical roles in enzymatic activities and cofactor formation. Changes in mitochondrial physiology may affect metal homeostasis and cofactor assembly.
FRONTIERS IN CELL AND DEVELOPMENTAL BIOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Laure Decamps, Derek B. Rice, Serena DeBeer
Summary: This study provides experimental evidence that the cofactor of the iron nitrogenase contains a carbide, making the Fe6C core a common feature among all nitrogenase cofactors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Asterios Charisiadis, Eleni Glymenaki, Aurelien Planchat, Sofia Margiola, Anna-Caroline Lavergne-Bril, Emmanouil Nikoloudakis, Vasilis Nikolaou, Georgios Charalambidis, Athanassios G. Coutsolelos, Fabrice Odobel
Summary: In this study, four different porphyrin-ruthenium dyads were utilized as sensitizers in both nand p-type DSSCs and DSPECs, demonstrating that dyads with ruthenium complexes exhibit improved performance in both systems.
Article
Chemistry, Multidisciplinary
Segun V. Obisesan, Cayla Rose, Byron H. Farnum, Christian R. Goldsmith
Summary: A Co(II) complex with the polydentate quinol-containing ligand H2qp1 acts as an efficient electrocatalyst for oxygen reduction. It selectively produces H2O without any additional electron-proton transfer mediators, whereas a related complex that substitutes a phenol for the quinol instead produces mostly H2O2 under the same conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Biochemistry & Molecular Biology
Horst Lechner, Gustav Oberdorfer
Summary: This article reviews the catalytic activity of non-metal cofactors in enzymes and the developments in derivatives of natural cofactors and new non-natural cofactors. It reports the current status of enzymes carrying organocatalysts as derivatives of natural cofactors or artificial ones and their application in the asymmetric synthesis of various compounds.
Article
Green & Sustainable Science & Technology
G. A. Correa, M. P. Loureiro, I Kuzniarska-Biernacka, C. Freire, S. L. H. Rebelo
Summary: In this study, nanostructured materials carrying Fe(III) porphyrins were prepared by ionic self-assembly in water and tested for the mimics of the six electron reduction activity of nitrite reductase. The catalytic activity of the materials showed a temperature-dependent or visible-light irradiation-dependent trend based on their composition.
MATERIALS TODAY SUSTAINABILITY
(2022)
Article
Engineering, Environmental
Xiaoxu Tan, Shiting Guo, Yuxian Wang, Yipeng Zhang, Hongxu Zhang, Chuanjuan Lu, Qian Wang, Ping Xu, Cuiqing Ma, Chao Gao
Summary: This study designed a costly cofactor-free enzymatic cascade to transform glucose into pyruvate, an important industrial compound. Only five enzymes and Mg2+ were required for pyruvate production. Under optimal conditions, 30.82 mM pyruvate was produced with a yield of 74.27% in 8 hours. In addition, acetoin, another important chemical, can also be produced from glucose through further manipulation of the enzymatic cascade, with a yield of 84.71% in 10 hours.
CHEMICAL ENGINEERING JOURNAL
(2023)
Review
Chemistry, Inorganic & Nuclear
Maheshwar S. Thakur, Neha Singh, Arti Sharma, Rohit Rana, A. R. Abdul Syukor, M. Naushad, Sunil Kumar, Manish Kumar, Lakhveer Singh
Summary: Macrocyclic ligand chemistry is a tool for designing molecules with inherent selective properties. Metal coordinated macrocyclic rings with stable conjugated systems and unique chelating properties have been effectively applied in organic transformations.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Engineering, Chemical
Zhibo Zhang, Xiangping Zhang, Xiaoyan Ji
Summary: This review summarizes the methods for enzymatic CO2 conversion, focusing on cofactor regeneration and the development of artificial cofactors, to provide a solution for sustainable large-scale enzymatic CO2 conversion.
Article
Chemistry, Physical
Rimsha Mehmood, Vyshnavi Vennelakanti, Heather J. Kulik
Summary: Researchers investigate substrate/active-site dynamics of nonheme iron halogenases like BesD and WelO5 using experimental and computational methods, revealing the importance of active-site configurational isomerization for selective halogenation in WelO5. They also find distinct patterns of substrate-protein interactions for these enzymes, and discuss how optimal substrate/active-site geometry plays a crucial role in facilitating chemoselectivity in halogenases. Their work demonstrates different substrate-dependent strategies used to promote selectivity in halogenases.
Article
Chemistry, Organic
Naziha Tarannam, Martin H. H. Voelkel, Stefan M. Huber, Sebastian Kozuch
Summary: A tellurium-based chalcogen-bond-catalyzed nitro-Michael reaction was found to be more effective than an analogous iodine-based halogen bond organocatalyst. Solvation effects explain the smaller energy span of the former.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Julian Stoesser, Elric Engelage, Stefan M. Huber
Summary: An improved general strategy for the synthesis of highly fluorinated biphenyls, terphenyls, and phenyl-substituted terphenyls using organozinc pivalates has been reported. The influence of several parameters on yield was investigated, showing scalability, versatility, and compatibility with commonly used phosphine ligands and palladium sources. This method does not require excess nucleophile for terphenyl synthesis and only a slight excess for the preparation of phenyl substituted terphenyls.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Martin H. H. Voelkel, Elric Engelage, Mykhailo Kondratiuk, Stefan M. Huber
Summary: In this study, the halogen bonding properties of 6-halo-2-pyridones and their pyridol tautomers were investigated both in the solid state and in solution. The results showed that halogen bonding indeed played a role in the packing motif in pyridone crystals, while no clear evidence for halogen bonding was found in solution.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Helgi Freyr Jonsson, Daniel Sethio, Julian Wolf, Stefan M. Huber, Anne Fiksdahl, Mate Erdelyi
Summary: Gold catalysis provides innovative organic transformations with high chemoselectivity under mild conditions. A silver-free route utilizing halogen bonding is presented for gold activation, reducing metal waste and enabling large-scale generation of complex molecules. The recyclability of gold is of supreme importance.
Article
Chemistry, Multidisciplinary
Tim Steinke, Patrick Wonner, Richard M. Gauld, Sascha Heinrich, Stefan M. Huber
Summary: This study investigates the activation of imines in a Povarov reaction using bidentate cationic chalcogen bond donors. Tellurium-based Lewis acids show superior catalytic properties compared to selenium-based catalysts. The activity of the chalcogen bonding donors is influenced by the strength of the binding anions, and the choice of solvent and catalyst affects the diastereomeric ratio of the product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Raffaella Papagna, Dana Kutzinski, Stefan M. Huber
Summary: In this study, recyclable polymer-bound halogen bonding catalysts were developed, which exhibited comparable catalytic activity to free halogen bond donors. This proof-of-principle research provides a foundation for the further development of sustainable halogen bonding organocatalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jana M. Holthoff, Elric Engelage, Adrian Ruff, Laura Galazzo, Enrica Bordignon, Stefan M. Huber, Robert Weiss
Summary: Carbenes with conjugatively connected redox system are capable of acting as auto-umpolung ligands and stabilizing open-shell species. In this study, the first neutral radical of such kind in the form of a dialkylamino-substituted bis(dicyanomethylene)cyclopropanide is described. The radical exhibits stability in solution and has been characterized through EPR measurements.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Raphael Robidas, Dominik L. Reinhard, Stefan M. Huber, Claude Y. Legault
Summary: This study analyzes and explains the higher Lewis acidity of cyclic diaryliodonium compounds using quantum-chemical calculations and energy decomposition analyses. The change in energy levels and hybridization of iodine's orbitals is the key factor leading to the increased Lewis acidity, resulting in more favorable electrostatic interaction and better charge transfer.
Article
Chemistry, Applied
Dhananjoy Pal, Tim Steinke, Lukas Vogel, Elric Engelage, Sascha Heinrich, Dana Kutzinski, Stefan M. Huber
Summary: This article describes the synthesis of a mixed chalcogen- and halogen-bond donor and provides a first indication of its catalytic activity in a benchmark reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Dominik L. Reinhard, Dana Kutzinski, Masahito Hatta, Elric Engelage, Stefan M. Huber
Summary: A new motif for iodine(III)-based halogen-bond donors was designed and evaluated as a potential catalyst through X-ray crystallography and benchmark catalytic activation.
Article
Chemistry, Multidisciplinary
Julian Stoesser, Elric Engelage, Debora Belmonte, Stefan M. M. Huber
Summary: Bromine-based halogen bond donors are weaker Lewis acids compared to iodinated counterparts, as demonstrated by NMR titrations and single crystal analyses. The binding affinity and recognition potential of neutral halogen bond donors are significantly decreased, especially in the presence of iodide salts. The three-point binding ability of phenyl-substituted-terphenyl-based donors towards orthoamide is also greatly reduced.
Article
Chemistry, Organic
Christoph J. Vonnemann, David Bulfield, Elric Engelage, Stefan M. Huber
Summary: A tweezer-like halogen bonding receptor capable of binding a neutral molecule (DABCO) from both sides is introduced. The coordination of DABCO and chloride ions is investigated in the solid state and in solution, and DFT calculations are used to explain the findings. This is the first molecular tweezer based solely on halogen bonding, which coordinates bifunctional substrates in a pincer-like fashion.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Julian Stoesser, Elric Engelage, Stefan M. Huber
Summary: Crystallographic studies were conducted to investigate the binding behavior of polyfluorinated twofold-iodinated triphenyl-based halogen bond donors. The obtained complexes showed strong halogen bonds with varying geometry and stoichiometry. Comparison with previously investigated fourfold-iodinated donors revealed differences in geometry, stoichiometry, and slight variations in halogen bond strength.
Article
Chemistry, Multidisciplinary
Cody Loy, Jana M. Holthoff, Robert Weiss, Stefan M. Huber, Sergiy V. Rosokha
Summary: Halogen-bonded complexes between halide anions and a cyclopropenylium-based anionic XB donor were characterized in solution for the first time, showing that halogen bonding is strong enough to overcome electrostatic repulsion. The formation constants of these complexes are comparable to others, but their UV-Vis spectra are determined by the electronic excitations within the XB donor.
Article
Chemistry, Organic
Revannath L. Sutar, Nikita Erochok, Stefan M. Huber
Summary: A series of cationic monodentate and bidentate iodo(benz)imidazolium-based halogen bond donors were employed as catalysts in a Mukaiyama aldol reaction. The bidentate XB donor showed strong performance even with low loading, while PF6 or OTf salts were inactive or showed background reaction through Lewis base catalysis. The stability of the catalyst over three consecutive cycles was confirmed through repetition experiments.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
