Article
Chemistry, Multidisciplinary
Yan Li, Chenxu Zheng, Zhi-Jiang Jiang, Jianbo Tang, Bencan Tang, Zhanghua Gao
Summary: A regioselective deuteration at the beta- and gamma-position of pyridines is achieved by using a combination of (KOBu)-Bu-t and DMSO-d(6), replenishing the prevailing alpha-deuteration of the pyridine systems. Preliminary mechanistic studies suggest that the dimsyl carbanion acts as one of the key intermediates.
CHEMICAL COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Da Zhao, Roland Petzold, Jiyao Yan, Dieter Muri, Tobias Ritter
Summary: Tritium labelling is a critical tool for pharmacokinetic and pharmacodynamic studies, and tritium gas is preferred for labelling due to its high isotopic purity. While heterogeneous catalysts like palladium supported on carbon are commonly used for tritiation reactions, their reaction mechanism can result in the reduction of other functional groups present in pharmaceuticals.
Article
Chemistry, Physical
Zengqi Lu, Xiaolong Fu, Jiamao Li, Jingwei Hou, Guangming Ran, Chengjian Xiao, Xiaolin Wang
Summary: A hydrophobic microscopic reaction environment was constructed through the modification of mesoporous silica, which helped improve the catalytic activity of the LPCE reaction. The Pt@SBA-15-tetramethyldisilazane catalyst, prepared by modifying the SBA-15 carrier and loading metal Pt, exhibited a superhydrophobic structure with a water contact angle of 158 degrees. This structure enhanced the catalytic performance and prevented catalyst deactivation. Experimental results showed that the catalyst had good catalytic activity in tritium water and maintained high activity after 30 days.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Applied
Daniel Becker, Dirk Bockfeld, Matthias Tamm
Summary: In this study, two complexes were obtained by reacting the bidentate [P,N] ligand with [Ir(COD)Cl] and adding different ligands, and further reaction yielded a diiridium tetrahydride. Crystal structure analysis of the three complexes revealed that the position of the hydrogen atoms in one of the complexes could be refined freely. Since the first complex is a validated catalyst, the performance of the two complexes in deuterium labeling reactions was compared.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Se Yeon Park, Jaehwan Kim, Haye Min Ko
Summary: An efficient chemoselective reduction of isatin derivatives has been achieved using B(C6F5)3 catalyst, benzyldimethylsilane, and H2O. Importantly, a small amount of water has been found to be a highly effective reaction promoter, reducing both the reaction time and temperature for the synthesis of indolin-3-ones. Furthermore, excellent deuterium incorporation has been achieved by catalytic alpha-deuteration of indolin-3-ones using B(C6F5)3 and D2O.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Qiuzhu Wang, Wenjuan Xiao, Honghui He, Jie Guo, Mengning Wang, Mengtao Ma, Binlin Zhao
Summary: A heterogeneous redox-neutral palladium-catalytic platform was developed for the synthesis of deuterated (hetero)arenes from (hetero)arenes via regioselective C(sp(2))-H thianthrenation using a commercially available and recyclable Pd/C catalyst. A wide range of deuterated compounds with high yields and excellent levels of deuterium incorporation could be obtained under these simple heterogeneous catalytic conditions, utilizing stable and easily handled DCOONa as a deuterium source. The late-stage deuteration of pharmaceuticals and bioactive molecules was also successfully achieved.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Zengqi Lu, Xiaolong Fu, Jingwei Hou, Lei Yue, Jiamao Li, Guangming Ran, Chengjian Xiao, Xiaolin Wang
Summary: To enhance hydrogen-water isotope exchange performance, a hydrophobic microenvironment was created within the catalyst support and a bimetal catalyst was utilized. The superhydrophobic catalyst exhibited significant improvement in performance. Adsorption/desorption tests demonstrated that the hydrophobic microenvironment increased the diffusion rate of reactants, while metal doping modification enhanced reactant concentration around the active site. Overall, the catalytic performance of the catalyst with the hydrophobic microenvironment exceeded that of normal hydrophobic catalysts, even with slightly diminished hydrophobicity.
CATALYSIS COMMUNICATIONS
(2023)
Article
Physics, Fluids & Plasmas
L. Frassinetti, C. Perez Von Thun, B. Chapman-Oplopoiou, H. Nystrom, M. Poradzinski, J. C. Hillesheim, L. Horvath, C. F. Maggi, S. Saarelma, A. Stagni, G. Szepesi, A. Bleasdale, A. Chomiczewska, R. B. Morales, M. Brix, P. Carvalho, D. Dunai, A. R. Field, J. M. Fontdecaba, H. J. Sun, D. B. King, D. Kos, E. Kowalska, B. Labit, M. Lennholm, S. Menmuir, E. Rachlew, D. I. Refy, P. A. Schneider, E. R. Solano, N. Vianello, M. Vecsei, JET Contributors
Summary: The study investigates the structure, transport, and stability of the pedestal from pure deuterium to pure tritium plasmas. Experimental and modeling results suggest a reduction in inter-edge localized mode transport and an improvement in pedestal stability from deuterium to tritium.
Article
Chemistry, Organic
Sara Kopf, Jiali Liu, Robert Franke, Haijun Jiao, Helfried Neumann, Matthias Beller
Summary: Deuterated organic molecules play a crucial role in life sciences and material research. Developing methods to selectively label compounds is of great importance. In this study, a general and applicable method for the selective deuteration of nitrogen-containing heterocycles using KOtBu as base and DMSO-d(6) as deuterium source is presented. Experimental and DFT mechanistic studies reveal that the reaction proceeds through deprotonation of the substrates by the dimsyl anion. The relative thermodynamic stability of the heterocycle anions determines the distribution and degree of deuteration.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Masud Monwar, Carlos Cruz, Jared Barr, Max McDaniel
Summary: The Phillips Cr(VI)/silica catalyst widely used in polyethylene production can be activated by nonolefinic hydrocarbons through a self-alkylation mechanism. Different hydrocarbon reductants lead to the formation of unique catalysts with distinctive ligands, influencing their polymerization activity and product specificity. This discovery opens up opportunities for creating novel varieties of Phillips catalysts.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Alexander Uttry, Sourjya Mal, Manuel van Gemmeren
Summary: The study describes the late-stage deuteration of free carboxylic acids and enables the functionalization of non-activated methylene beta-C(sp(3))-H bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Jose B. Roque, Tyler P. Pabst, Paul J. Chirik
Summary: The use of bis(silylene)pyridine cobalt(III) dihydride boryl as a precatalyst enables efficient hydrogen isotope exchange reactions, including deuterium incorporation at sterically hindered sites and high chemoselectivity towards aryl halides.
Article
Nanoscience & Nanotechnology
Xiaochong Xue, XinXin Chu, Mingjun Zhang, Fei Wei, Chaofei Liang, Jie Liang, Jinglin Li, Wenyu Cheng, Ke Deng, Wei Liu
Summary: This study demonstrates the high separation efficiency of single-layer graphene membranes in proton exchange membrane water electrolysis. However, the enhanced separation efficiency can be attributed to the decorated catalyst rather than the graphene itself.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Emeline Appert, Agnes Martin-Mingot, Omar Karam, Fabien Zunino, Bastien Michelet, Fodil Bouazza, Sebastien Thibaudeau
Summary: The field of medicinal chemistry is currently experiencing a deuterium rush, and the exchange of aromatic hydrogen isotopes is one of the most researched strategies. However, the use of superacidic conditions has been overlooked. This study shows that using TfOD as the reaction medium enables late-stage polydeuteration of pharmaceuticals with various functional groups, complementing existing procedures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Kazuhiro Okamoto, Ryosuke Higuma, Kensuke Muta, Keita Fukumoto, Yuta Tsuchihashi, Yosuke Ashikari, Aiichiro Nagaki
Summary: In this study, H-D exchange of one methylene proton was achieved in various dihalomethanes. Highly unstable carbenoid intermediate generation and its decomposition were successfully controlled under high flow-rate conditions. Monofunctionalization of diiodomethane afforded various building blocks, and diverted functionalization of monodeuterated diiodomethane produced products with isotope labeling and monodeuteration.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)