Article
Chemistry, Organic
Keisuke Takahashi, Shunya Kudo, Kiharu Kawamura, Taichi Kusakabe, Shoko Kikkawa, Isao Azumaya, Keisuke Kato
Summary: The proposed structure of mohangic acid C (3) was synthesized through a series of reactions, which selectively introduced specific functional groups and constructed the overall framework of the molecule.
Article
Chemistry, Multidisciplinary
Enrico Bergamaschi, Danijela Lunic, Liam A. McLean, Melissa Hohenadel, Yi-Kai Chen, Christopher J. Teskey
Summary: This study demonstrates, for the first time, the ability to use light to distinguish between ketones and carboxylic acids in more complex molecules. By utilizing different activation modes, a single catalytic system can be used for hydroboration, with chemoselectivity dictated solely by the presence or absence of visible light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Taichi Yumura, Takeshi Nanjo, Yoshiji Takemoto
Summary: This article reports an efficient hybrid photo-redox catalyst that enables radical cyclization of unsaturated carboxylic acids previously requiring harsh reaction conditions. Mechanistic studies have revealed that the catalyst promotes single electron transfer and leads to unconventional cis-trans isomerization of the cyclobutane rings.
Article
Chemistry, Organic
Xin Li, Weili Si, Zhanhui Liu, Haitao Qian, Tingxue Wang, Shengnan Leng, Jinwei Sun, Yan Jiao, Xuan Zhang
Summary: A photocatalyst- and metal-free approach is presented in this study, enabling the generation of an alkyl radical from a primary alcohol and subsequent C(sp(3))-C(sp(3)) bond formation with an activated olefin. This protocol for converting a C-OH bond to a C-C bond exhibits high functionality tolerance and can be successfully utilized in late-stage functionalization of pharmaceuticals.
Article
Chemistry, Multidisciplinary
Oscar M. F. Lama, Diego A. Roa, Alma Arevalo, Juventino J. Garcia
Summary: The hydrodeoxygenation (HDO) of different fatty acids (FAs) was successfully achieved using commercially available nickel(II) compounds as catalysts and silanes as reducing agents under mild reaction conditions. By fine-tuning the reaction conditions and using relatively mild conditions without additives, high conversions (83% to >=99%) and good selectivity were obtained for the carboxylic group reduction of fatty acids, yielding aldehydes, alcohols, and hydrocarbons. The reaction mechanism was investigated using a synthesized and characterized reaction intermediate [Ni(C15H31COO)(2)(H2O)(2)], which demonstrated as an active catalyst.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Yifan Li, Changhui Dai, Shentong Xie, Ping Liu, Peipei Sun
Summary: This study presents an efficient visible-light-induced decarboxylative coupling reaction of N-protecting alpha-amino acids with heterocycles for the generation of aminoalkylated heterocycles. A series of aminoalkylated heterocycles were obtained in moderate to good yields, utilizing an inexpensive organic photocatalyst under transition-metal-free conditions.
Article
Chemistry, Organic
Feng Jiang, Tengfei Meng, Ying Zhou, Zhenying Xiong, Yupei Zhao, Wengang Guo
Summary: We report an enantio- and diastereodivergent synthesis of enantioenriched fluorenes with broad substrate scope and high enantioselectivity (up to 99% ee) under low catalyst loading (0.1 mol %). The success of this method lies in the pseudo-diastereodivergent desymmetrization of stereoisomers of meso-epoxides enabled by the same organocatalyst. Furthermore, some of the chiral fluorenes obtained exhibit high fluorescence quantum yields (up to 76.6%), as evidenced by photophysical properties studies.
Article
Chemistry, Multidisciplinary
Yu Zhang, Prakash Kumar Sahoo, Peng Ren, Yuman Qin, Robin Cauwenbergh, Philippe Nimmegeers, Gandhi SivaRaman, Steven Van Passel, Andrea Guidetti, Shoubhik Das
Summary: A transition metal-free method has been reported for the selective functionalization of benzylic C(sp(3))-H bonds using alcohols and carboxylic acids as nucleophiles. This straightforward and general approach has provided various benzylic ethers and esters, including twelve pharmaceutically relevant compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Tatiana Chenet, Annalisa Martucci, Mirco Cescon, Giulia Vergine, Giada Beltrami, Lara Gigli, Matteo Ardit, Massimo Migliori, Enrico Catizzone, Girolamo Giordano, Luisa Pasti
Summary: The adsorption of L-lysine on two ZSM-5 materials with different Si/Al ratios revealed that the aluminum content plays a crucial role in tuning the adsorption process. Higher Si/Al ratios led to lower saturation capacity and binding constants. High resolution X-ray diffraction data showed that the adsorption of L-lysine in ZSM-5 is a surface-confined supramolecular self-assembly process, influenced by pH and hydration state.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Physical
Jun-Fei Gu, Cheng Chen, Zhong-Hui Zheng, Jing Hang, Wei Sang, Ji-Chao Wang, Ye Yuan, Somboon Chaemchuen, Francis Verpoort
Summary: In this study, it was found that ZIF-8, a representative Zn-based metal-organic framework, exhibits high porosity, good stability, and large surface area. ZIF-8 shows promising potential in catalyzing the acceptorless dehydrogenation of alcohols to carboxylates and demonstrates good reusability. Additionally, KOH plays a crucial role in this catalytic process.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ana M. Garcia, Michele Melchionna, Ottavia Bellotto, Slavko Kralj, Sabrina Semeraro, Evelina Parisi, Daniel Iglesias, Paola D'Andrea, Rita De Zorzi, Attilio V. Vargiu, Silvia Marchesan
Summary: Self-assembling peptides with proline as a beta-breaker and diphenylalanine motif were studied for their ability to form diverse nanostructures. The stereo-configuration of amino acids played a crucial role in directing these peptides to assemble into nanoparticles, nanotapes, or fibrils. Additionally, the study found that heterochirality could strategically interfere with pathological processes, potentially offering future therapeutic applications with resistance to degradation and biocompatibility.
Article
Chemistry, Organic
Donghui Guo, Qiupeng Peng, Bei Zhang, Jian Wang
Summary: The novel method described in this report allows for the atroposelective generation of axially chiral amino esters using hemiaminals formed in situ, with a wide substrate scope, good functional group tolerance, and rapid assembly of axially chiral amino esters with high enantioselectivities in good to high yields.
Article
Chemistry, Multidisciplinary
Cayo Lee, Brodie J. Thomson, Glenn M. Sammis
Summary: A novel method for the generation of thionyl fluoride (SOF2) has been developed, allowing access to both aliphatic and aromatic acyl fluorides in moderate to high yields. The method shows potential for amino acid couplings and peptide synthesis, both in liquid phase and solid phase, without the need for column chromatography.
Article
Chemistry, Applied
Ken Okuno, Bun Chan, Seiji Shirakawa
Summary: Catalytic kinetic resolution is a reliable method for enantioselective synthesis of chiral molecules. However, it is challenging to perform kinetic resolution on racemic compounds with similar substituents at a chiral center. In this study, a kinetic resolution of a-allyl-a-propargyl carboxylic acids was achieved using a chiral bifunctional sulfide catalyst. The utility of the resulting optically active compounds was also demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Nian Li, Yantao Li, Xiaopeng Wu, Chengjian Zhu, Jin Xie
Summary: Deuterated chemicals are indispensable in pharmaceutical engineering, material science, and synthetic chemistry. Radical deuterium-labelling technology has seen rapid growth with the development of radical chemistry, leading to the discovery of diverse, mild, cheap, and efficient strategies for deuterium atom installation. This review summarizes recent achievements of radical deuteration, categorized by reaction types.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Tobias Biberger, Stephan N. Hess, Markus Leutzsch, Alois Fuerstner
Summary: In this study, a new hydrogenation reaction transformation was reported, where propargyl alcohol derivatives were converted to cyclopentene products using [(CpRu)-Ru-X(MeCN)(3)]PF6 as catalyst. It was also discovered that rearrangements leading to other organic compounds could occur when the transient carbene carried appropriate substituents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Carla Obradors, Benjamin Mitschke, Miles H. Aukland, Markus Leutzsch, Oleg Grossmann, Sebastian Brunen, Sebastian A. Schwengers, Benjamin List
Summary: Since early 2020, scientists have been striving to find effective solutions to combat SARS-CoV-2, focusing on developing reliable vaccines and repurposing drugs. However, the current synthetic routes for Remdesivir, the most widely used therapeutic during the early stages of infection, face challenges in cost-effective supply to patients. In this study, researchers have developed a straightforward method for adding (hetero)arenes to unprotected sugars, significantly expediting the synthesis of Remdesivir precursor GS-441524.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tobias Biberger, Nils Noethling, Markus Leutzsch, Christopher P. Gordon, Christophe Coperet, Alois Fuerstner
Summary: In the investigation of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions, a thermally robust anionic dinuclear sigma-dihydrogen complex was found. This complex, formed by the reaction of [(IPr)(eta(6)-cymene)RuCl2] with H-2 under UV-irradiation, is a rare example of anionic sigma-complexes lacking any structural attributes to counterbalance the negative charge and prevent metal center insertion into ligated H-2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jie Ouyang, Rajat Maji, Markus Leutzsch, Benjamin Mitschke, Benjamin List
Summary: Here, we report the design of a highly enantioselective, catalytic (4 + 3) cycloaddition reaction enabled by strong and confined IDPi Lewis acids. This reaction allows the synthesis of novel compounds with multiple stereocenters from gem-dialkyl 2-indolylalcohols and dienolsilanes. The method exhibits broad substrate scope and versatile downstream chemical modifications. Density functional theory-supported mechanistic studies reveal the significance of the in-situ generated silylium species in an overall concerted yet asynchronous cycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Hui Zhou, Yu Zhou, Han Yong Bae, Markus Leutzsch, Yihang Li, Chandra Kanta De, Gui-Juan Cheng, Benjamin List
Summary: Enzymatic stereoselectivity is often better than most chemical catalysts in the conversion of small substrates. A recent study has reported the development of broadly applicable confined organocatalysts for the highly enantioselective cyanosilylation reaction. The selectivity (98:2 enantiomeric ratio) of the catalyst towards the pharmaceutically relevant product exceeds any other catalyst class, including engineered biocatalysts.
Article
Chemistry, Multidisciplinary
Clement Ghiazza, Lucas Wagner, Sergio Fernandez, Markus Leutzsch, Josep Cornella
Summary: Among the tools available to chemists for drug design of bioactive compounds, the bioisosteric replacement of atoms or groups of atoms is the cornerstone of modern strategies. The enzymatic deaminative hydroxylation remains unmatched despite the interest in amino-to-hydroxyl interchange. The study reports a safe and user-friendly procedure using a pyrylium tetrafluoroborate salt to selectively convert aminoheterocycles to hydroxylated analogues. Mechanistic experiments revealed an unusual mechanism for this aromatic substitution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiuxiu Yang, Edward J. Reijerse, Nils Noethling, Daniel J. SantaLucia, Markus Leutzsch, Alexander Schnegg, Josep Cornella
Summary: In this study, we synthesized, isolated, and characterized two cationic organobismuth(II) compounds with N,C,N pincer frameworks, which mimic crucial intermediates in bismuth radical processes. X-ray crystallography revealed a monomeric Bi(II) structure, and SQUID magnetometry combined with NMR and EPR spectroscopy provided evidence for a paramagnetic S = 1/2 state. High-resolution multifrequency EPR at the X-, Q-, and W-band allowed for precise assignment of the full g- and 209Bi A-tensors. Experimental data and DFT calculations showed that both complexes are metal-centered radicals with minimal delocalization onto the ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rajat Maji, Santanu Ghosh, Oleg Grossmann, Pinglu Zhang, Markus Leutzsch, Nobuya Tsuji, Benjamin List
Summary: In this study, a catalytic asymmetric hydrolactonization using a confined imidodiphosphorimidate (IDPi) Bronsted acid catalyst is reported. The method is simple, scalable, and compatible with a wide variety of substrates. The mechanism and enantioselectivity of this reaction are elucidated through in-depth physicochemical and DFT analyses.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hui Zhou, Roberta Properzi, Markus Leutzsch, Paola Belanzoni, Giovanni Bistoni, Nobuya Tsuji, Jung Tae Han, Chendan Zhu, Benjamin List
Summary: Chiral organosilanes are not naturally occurring and are therefore rare. However, a new synthetic approach using racemic silanes as starting materials has been developed, which expands the range of accessible Si-stereogenic compounds. This approach involves the use of strong and confined imidodiphosphorimidate (IDPi) catalysts to enable the dynamic kinetic asymmetric transformation (DYKAT) of racemic allyl silanes, leading to the formation of Si-stereogenic silyl ethers. The products can be easily converted into enantiopure monohydrosilanes. A proposed mechanism involves the epimerization of a catalyst-bound intermediate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Joyce A. A. Grimm, Hui Zhou, Roberta Properzi, Markus Leutzsch, Giovanni Bistoni, Johanna Nienhaus, Benjamin List
Summary: The discovery of a highly efficient and selective catalyst enables the conversion of natural or synthetic neral to (1R,6S)-trans-isopiperitenol, providing sustainable routes to menthol and cannabinoids.
Article
Multidisciplinary Sciences
Yue Pang, Nils Noethling, Markus Leutzsch, Liqun Kang, Eckhard Bill, Maurice van Gastel, Edward Reijerse, Richard Goddard, Lucas Wagner, Daniel SantaLucia, Serena DeBeer, Frank Neese, Josep Cornella
Summary: In this work, the synthesis and characterization of a monocoordinate bismuthinidene compound with a rigid and bulky ligand were reported. Despite showing diamagnetic properties in all magnetic measurements, multiconfigurational quantum chemical calculations revealed that the compound's ground state is dominated by a spin triplet. The apparent diamagnetism is explained by an extremely large spin-orbit coupling-induced positive zero-field splitting.
Article
Chemistry, Multidisciplinary
Hye Won Moon, Feng Wang, Kalishankar Bhattacharyya, Oriol Planas, Markus Leutzsch, Nils Noethling, Alexander A. Auer, Josep Cornella
Summary: This research investigates the transfer hydrogenation of azoarenes catalyzed by bismuth through experimental and computational studies. The role of protic and hydridic hydrogens in the reaction is identified through kinetic analysis and reactivity studies using p-trifluoromethylphenol and pinacolborane. The possibility of bismuth-ligand cooperativity is also assessed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Davide Spinnato, Markus Leutzsch, Feng Wang, Josep Cornella
Summary: In this article, a method to transform isoxazoles and oxadiazoles into pyrazoles and 1,2,4-triazoles in one step using a copper catalyst is provided. The method allows for rapid evaluation of different five-membered azole scaffolds, avoiding de novo synthesis of the molecule of interest.
Article
Chemistry, Multidisciplinary
Takuya Tsuruta, Davide Spinnato, Hye Won Moon, Markus Leutzsch, Josep Cornella
Summary: We present a dual-catalyzed C-H trifluoromethylation of (hetero)-arenes using CF3SO2Cl under light irradiation. The reaction enables direct modification of various heterocycles with different functional groups. Structural and computational studies reveal that the reaction proceeds through an open-shell redox reaction at bismuth, involving three unusual elementary steps.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)