Review
Chemistry, Multidisciplinary
Sara Kopf, Florian Bourriquen, Wu Li, Helfried Neumann, Kathrin Junge, Matthias Beller
Summary: Organic compounds labeled with hydrogen isotopes are crucial in drug discovery and development in the pharmaceutical industry. Recent advancements have been made in methodologies for isotopic enrichment of organic molecules, including hydrogen isotope exchange reactions, isotopically labeled analogues of organic reagents, and other transformations with isotope incorporation.
Article
Chemistry, Multidisciplinary
Tao He, Hendrik F. T. Klare, Martin Oestreich
Summary: Superelectrophilic silylium/arenium ions are effective in exhaustivedeuteration of electron-deficient aryl halides. Using inexpensive C6D6as the deuterium source, excellent degrees of deuteriumincorporation were achieved under ambient conditions. This method allows the preparation of expensive or noncommercially available NMR solvents.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Kwihwan Park, Naoki Oka, Yoshinari Sawama, Takashi Ikawa, Tsuyoshi Yamada, Hironao Sajiki
Summary: We developed a platinum-catalyzed deuteration reaction using deuterium oxide as a deuterium source, which selectively deuterated tert-allylic alcohols with good deuterium content. The obtained deuterium-labeled allylic alcohols were further transformed into various deuterium-labeled building blocks without degradation of the original deuterium content.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Xue-Ya Gou, Xin-Yu Zhu, Bo-Sheng Zhang, Yong-Min Liang
Summary: In recent years, the synthesis of C-aryl glycosides through C-H functionalization has gained significant attention due to its efficiency and economy. This review focuses on the synthesis of C-aryl glycosides using C-H arylation of glycosides and C-H glycosylation of arenes, highlighting their regioselectivity and diastereoselectivity. It is observed that newly developed C-H glycosylation reactions exhibit better selectivity than traditional Friedel-Crafts glycosylation, with milder reaction conditions that are compatible with acid-sensitive protective groups. However, remote C-H glycosylation of aromatic hydrocarbons remains a relatively unexplored area that requires further research.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xiang-Ting Min, Yong-Kang Mei, Bing-Zhi Chen, Li-Bowen He, Ting-Ting Song, Ding-Wei Ji, Yan-Cheng Hu, Boshun Wan, Qing-An Chen
Summary: An efficient deuterium labeling technique using Rh-catalyzed decarbonylation of aldehydes with D2O is developed, which shows great potential in the field of deuterated drug candidates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Guang-Qi Hu, Jing-Wen Bai, En-Ci Li, Kai-Hui Liu, Fei-Fei Sheng, Hong-Hai Zhang
Summary: A new method for deuterating (hetero)aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source is disclosed in this study, which is highly efficient and easy to manipulate. In comparison to traditional multistep syntheses, this method allows for one-step deuterium labeling of various bioactive druglike molecules and key intermediates of functional materials. Additionally, this method demonstrates unique site-selectivity in comparison to existing transition-metal-catalyzed processes, leading to multideuterated (hetero)aryl bromides in one step.
Article
Chemistry, Physical
Jiahao Liu, Yinwu Li, Jingxing Jiang, Yan Liu, Zhuofeng Ke
Summary: The study systematically provided mechanistic scenarios including boryl-directed (BD) oxidative addition, nondirected (nonBD) oxidative addition, and boryl-metal cooperation via B-hydrido type (BHMC) or B-carbanion type (BCMC) mechanisms to elucidate the role of a Lewis acidic boryl group in selective o-C-H activation of pyridine with PBP-Ir complexes. The results suggest the plausibility of BD and BCMC mechanisms, while nonBD and BHMC mechanisms are less preferred due to weak interactions and large distortions. Various PBP-Ir complexes have been evaluated to further explore the guidelines of this mechanistic understanding for the rational design of Lewis acid-transition-metal catalysts.
Article
Chemistry, Physical
Vincent Desrosiers, Samantha M. Knight, Frederic-Georges Fontaine
Summary: Alkenyl boronates are commonly used reagents in organic synthesis for the formation of crucial bonds. This study introduces a metal-free isodesmic borylation strategy for the C-H borylation of electron-rich olefins, using 2-mercaptoimidazole compounds as efficient catalysts. The borylated compounds can be further functionalized in one-pot transformations, demonstrating the versatility and tolerance of this method.
Article
Chemistry, Multidisciplinary
Qi Chen, Qing Liu, Jie Xiao, Xuebing Leng, Liang Deng
Summary: This paper presents a catalytic method for the preparation of deuterated NHCs, using a coordinatively unsaturated Ru NHC catalyst to achieve selective deuterium labeling. Mechanistic studies revealed the high regio-selectivity of this catalytic system, offering a new approach for the synthesis of deuterated NHCs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Karunanidhi Murali, Luana A. Machado, Renato L. Carvalho, Leandro F. Pedrosa, Rishav Mukherjee, Eufranio N. Da Silva Junior, Debabrata Maiti
Summary: C-H functionalization has made significant advancements in synthetic organic chemistry, offering promising prospects in drug development and molecular architecture. The employment of novel metal catalysts and metal-free organic ligands has enabled selective activation of C-H bonds, overcoming previous challenges faced by chemists.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Adrian Tlahuext-Aca, John F. Hartwig
Summary: A new phosphine-ligated, silver-carbonate complex catalyst has been developed for the site-selective deuteration of C-H bonds in five-membered aromatic heterocycles and active pharmaceutical ingredients. The reactions occur using CH3OD as a low-cost source of the isotope and show tolerance towards a wide range of functional groups in both polar and nonpolar solvents. Mechanistic experiments support C-H bond cleavage from a phosphine-ligated, silver-carbonate intermediate as the rate-determining step of the catalytic cycle.
Article
Multidisciplinary Sciences
Yanjun Li, Ziqi Ye, Yu-Mei Lin, Yan Liu, Yumeng Zhang, Lei Gong
Summary: The development of a photochemical system using an aryl-amine-based photocatalyst and a common disulfide co-catalyst enables efficient deuteration of various organic chlorides at room temperature in air. This environmentally-friendly method allows for site-selective labeling and direct exchange of drug molecules.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Dhanushka Darshana, Sanya Sureram, Chulabhorn Mahidol, Somsak Ruchirawat, Prasat Kittakoop
Summary: This study presents a simple method for the generation of deuterium halides, applicable to various substrates for acid-catalyzed and organocatalytic deuterium reactions. It also demonstrates a gram-scale chromatography-free synthesis of deuterated compounds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Meeree Kim, G. Hwan Park, Sohyeon Seo, Viet Quoc Bui, Yunhee Cho, Yeseul Hong, Yoshiyuki Kawazoe, Hyoyoung Lee
Summary: This study focuses on the role of countercations during ligand exchange on the surfaces of colloidal transition metal dichalcogenide (TMD) nanocrystals. The countercations intercalated between TMD layers were found to enhance the electrochemical hydrogen evolution reaction (HER) catalytic activity by improving charge transfer with the electrolyte. Exchange of surface functionalities with anionic ligands and introduction of countercations were both found to be important in enhancing the overall catalytic activity of the TMD nanocrystals.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Review
Chemistry, Physical
Prabhat Kumar Baroliya, Jaishri Chopra, Tanay Pal, Siddhartha Maiti, Shaeel Ahmed Al-Thabaiti, Mohamed Mokhtar, Debabrata Maiti
Summary: Supported metal nanoparticles have become an essential research area in catalysed chemical transformations, providing sustainable processes and efficient tuning of reactivity and recyclability. Various support materials have been investigated for their benefits in C-H functionalization, aiming to design efficient catalytic systems for future research.
Article
Chemistry, Multidisciplinary
Maria Galiana-Cameo, Marina Borraz, Yaroslava Zelenkova, Vincenzo Passarelli, Fernando J. Lahoz, Jesus J. Perez-Torrente, Luis A. Oro, Andrea Di Giuseppe, Ricardo Castarlenas
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Inorganic & Nuclear
Ana Luque, Amaia Iturmendi, Laura Rubio-Perez, Julen Munarriz, Victor Polo, Vincenzo Passarelli, Manuel Iglesias, Luis A. Oro
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Ramon Azpiroz, Ingo Greger, Luis A. Oro, Vincenzo Passarelli, Ricardo Castarlenas, Jesus J. Perez-Torrente
Summary: Iridium(I) N-heterocyclic carbene complexes have been synthesized and found to efficiently catalyze the hydroalkenylation of aromatic and aliphatic terminal alkynes with 2-vinylpyridine, leading to the formation of 2-(4R-butadienyl)pyridines as the major reaction products. Additionally, minor reaction products including (Z)-2-butadienyl-5R-pyridine derivatives have been obtained from the 1Z,3gem-butadienyl hydroalkenylation products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Maria Galiana-Cameo, Vincenzo Passarelli, Jesus J. Perez-Torrente, Andrea Di Giuseppe, Ricardo Castarlenas
Summary: A series of rhodium complexes, both neutral and cationic, have been reported with different synthetic pathways for catalytic reactions, exhibiting varying activities in the phenylacetylene-methanol transformations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Maria Galiana-Cameo, Asier Urriolabeitia, Eduardo Barrenas, Vincenzo Passarelli, Jesus J. Perez-Torrente, Andrea Di Giuseppe, Victor Polo, Ricardo Castarlenas
Summary: Mononuclear square-planar Rh complexes were synthesized for alkyne dimerization, with N,O-pyridonato derivatives exhibiting high catalytic activity. Mechanistic studies revealed that a pyridonato-based metal-ligand cooperative proton transfer enhances catalytic activity, while protonation of the alkyne at the terminal position determines product selectivity in the reaction process.
Article
Chemistry, Inorganic & Nuclear
Roberta Colaiezzi, Andrea Lazzarini, Francesco Ferella, Valentina Paolucci, Andrea Di Giuseppe, Marcello Crucianelli
Summary: Three novel active and stable magnetic nanocatalysts were prepared for the selective oxidation of olefins. These heterogeneous systems showed excellent catalytic performance in both organic and aqueous solvents, with the ability to be recycled and reused over five runs without significant decrease in activity. The good magnetic properties of these catalytic systems demonstrate their versatility and robustness.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Maria Galiana-Cameo, Raul Romeo, Asier Urriolabeitia, Vincenzo Passarelli, Jesus J. Perez-Torrente, Victor Polo, Ricardo Castarlenas
Summary: The dinuclear complex [Rh(eta-C1)(eta(2)-coe)(IPr)](2) serves as an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations suggest a hydride-free pathway involving intramolecular oxidative protonation of a pi-alkyne by a kappa N-1-hydroxypyridine ligand. The release of the alkenyl ether is considered the rate-determining step in the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Pablo Hermosilla, Daniel Funes-Hernando, Ricardo Castarlenas, Andrea Di Giuseppe, Ramon Azpiroz, Eugenio Vispe, Jesus J. Perez-Torrente
Summary: The catalytic system of [Rh(mu-Cl)(IPr)(eta 2-coe)]2/pyridine efficiently facilitates the polyhydrothiolation reaction between dithiols and dialkynes, resulting in the formation of sulfur-rich poly(vinylidene sulfide)s with high molecular weights and high vinylidene sulfide content. The combination of different types of dithiols and dialkynes allows the preparation of poly(vinylidene sulfide)s with varying properties.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Romane Manguin, Maria Galiana-Cameo, Tanakorn Kittikool, Cecile Barthes, Jompol Thongpaen, Etienne Bancal, Sonia Mallet-Ladeira, Sirilata Yotphan, Ricardo Castarlenas, Marc Mauduit, Jean-Baptiste Sortais, Olivier Basle
Summary: This article discusses the synthesis and characterization of a new series of iridium complexes with NHC-carboxylate ligands, which exhibit efficient catalytic activities in dehydrogenative directed C-H silylation of arenes, with excellent ortho-selectivity control.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Roberta Colaiezzi, Chiara Saviozzi, Nicola di Nicola, Stefano Zacchini, Guido Pampaloni, Marcello Crucianelli, Fabio Marchetti, Andrea Di Giuseppe, Lorenzo Biancalana
Summary: The reductive N-monomethylation of nitroarenes can be conveniently realized in one-pot using methanol as the reductant, methylating agent, and solvent. New ruthenium(II) arene complexes were developed as efficient catalytic precursors for the tandem reduction/N-methylation of aromatic nitrocompounds with methanol, starting from commercially available and inexpensive dioxime ligands.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Amy E. Kynman, Luca K. Elghanayan, Addison N. Desnoyer, Yan Yang, Laurent Severy, Andrea Di Giuseppe, T. Don Tilley, Laurent Maron, Polly L. Arnold
Summary: The controlled functionalization of a single fluorine in a CF3 group is difficult and rare. This study demonstrates the importance of metal-ligand cooperativity in organometallic photocatalysis.
Article
Chemistry, Inorganic & Nuclear
Mert Olgun Karata, Bulent Alici, Vincenzo Passarelli, Ismail Ozdemir, Jesus J. Perez-Torrente, Ricardo Castarlenas
Summary: A series of iridium(I) complexes have been synthesized and their structural changes in solid state and solution were observed experimentally. Characterization of the complexes by NMR and determination of thermodynamic parameters and catalytic properties revealed their potential applications in catalyzing alkyne reactions.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Pilar Garcia-Orduna, Israel Fernandez, Luis A. Oro, Francisco J. Fernandez-Alvarez
Summary: The reported Ir-Si bond distances are in the lowest limit found in the Cambridge Structural Database, with the ionic contribution being mainly responsible for the observed Ir-Si bond shortening.
DALTON TRANSACTIONS
(2021)
