Article
Chemistry, Physical
Somayyeh Gandomkar, Raquel Rocha, Frieda A. Sorgenfrei, Lia Martinez Montero, Michael Fuchs, Wolfgang Kroutil
Summary: The study implemented an oxidation step relying on a single PQQ-dependent dehydrogenase to achieve oxidation of both enantiomers. The stereoselective amination of the alpha,beta-unsaturated ketone intermediate was achieved using transaminases, and enantio-convergent amination of the racemic allylic alcohols was successfully completed in a sequential cascade.
Article
Chemistry, Organic
P. Veeraraghavan Ramachandran, Abdulkhaliq A. Alawaed, Henry J. Hamann
Summary: Deoxyhalogenation of aryl aldehydes, ketones, carboxylic acids, and esters has been achieved by using a suitable metal halide Lewis acid as a carbonyl activator and halogen carrier, in combination with borane-ammonia as the reductant. Selectivity is achieved by matching the stability of the carbocation intermediate with the effective acidity of the Lewis acid. Substituents and substitution patterns significantly influence the choice of solvent/Lewis acid combination. Logical combinations of these factors have also been applied for the regioselective conversion of alcohols to alkyl halides.
Article
Chemistry, Organic
Soumen Barik, Rohan Chandra Das, Kuruva Balanna, Akkattu T. Biju
Summary: Chiral NHC-catalyzed kinetic resolution allows the synthesis of C-N axially chiral N-aryl aminomaleimides via remote chirality control. The reaction shows high stereoselectivity, yielding the desired product, and studies on C-N bond rotation and temperature dependence are provided.
Article
Chemistry, Multidisciplinary
Weijin Wang, Xiaoxue Yang, Rongheng Dai, Zixi Yan, Jialiang Wei, Xiaodong Dou, Xu Qiu, Hongliang Zhang, Chen Wang, Yameng Liu, Song Song, Ning Jiao
Summary: The electrophilic halogenation of arenes is a common method to prepare aryl halides, but reactions of arenes with electron-withdrawing substituents usually require harsh conditions and have limited substrate scopes. This study describes a mild protocol for the halogenation of arenes with electron-withdrawing substituents catalyzed by Bronsted acid, providing an efficient method for the synthesis of aryl halides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jun Zhang, Yaqing Ma, Fangfang Zhu, Jinping Bao, Qiaqing Wu, Shu-Shan Gao, Chengsen Cui
Summary: In this study, engineered imine reductases (IREDs) were obtained through semi-rational design, with residues W234 and F260 identified to enhance and reverse the stereoselectivity, respectively. Two enantio-complementary variants, S241L/F260N and I149D/W234I, showed excellent stereoselectivity and were used as valuable biocatalysts for synthesizing pyrrolidinamines. Their application in the short synthesis of key intermediates for potential drug molecules leniolisib and JAK1 inhibitor 4 was demonstrated.
Article
Chemistry, Multidisciplinary
Linghua Wang, Saima Perveen, Yizhao Ouyang, Shuai Zhang, Jiao Jiao, Gang He, Yong Nie, Pengfei Li
Summary: A novel nickel(II)-carborane complex catalyst has been reported in this study, allowing for selective carbene transfer reactions under low catalyst loading and mild conditions, effective for various types of reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yu-Fang Tan, Ya-Nan Zhao, Dan Yang, Jin-Feng Lv, Zhi Guan, Yan-Hong He
Summary: We present a new and highly selective electrochemical method for synthesizing beta-iodoesters from alkenes. This reaction takes place in an undivided cell under constant current conditions, eliminating the need for any additives, catalysts, oxidants, or sacrificial reagents. Tetrabutylammonium iodide, an inexpensive and readily available electrolyte, serves as both an electrolyte and an iodine source. The reaction exhibits high selectivity, good functional group tolerance, and yields products up to 98%. It can also be applied to chloro- and bromofunctionalization of alkenes. The successful modification of drugs and natural products demonstrates the potential utility of this approach.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yu-Fang Tan, Ya-Nan Zhao, Dan Yang, Jin-Feng Lv, Zhi Guan, Yan-Hong He
Summary: We present a new and highly selective electrochemical method for synthesizing fi-iodoesters by difunctionalization of alkenes. This reaction is conducted in an undivided cell under constant current conditions without the need for any additives, catalysts, oxidants, or sacrificial reagents. Inexpensive and readily available tetrabutylammonium iodide acts as both an electrolyte and an iodine source. The reaction exhibits high selectivity and good functional group tolerance, yielding products up to 98%. This method is not only applicable to iodofunctionalization but also chloro- and bromofunctionalization of alkenes. The successful modification of drugs and natural products demonstrates the potential utility of this approach.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jordan Francois, Jordan Rio, Erwann Jeanneau, Marie-Eve L. Perrin, Maiwenn Jacolot, Pierre-Adrien Payard, Florence Popowycz
Summary: Taking advantage of our preliminary observations, we successfully achieved the direct C-C borrowing hydrogen functionalization on isosorbide using an Ir-based organometallic homogeneous catalyst with excellent diastereocontrol. The reaction involves a catalytic dehydrogenation, in situ aldol condensation/crotonisation, and a catalytic dehydrogenation to yield the desired homologated product. Through a computational mechanistic investigation, we elucidated the stereoelectronic effects and the roles of the Na counter-cation in guiding the hydride addition and coordinating the substrate's oxygen atoms, thus rationalizing the experimental selectivity at the molecular level.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jia-Le Zheng, Fei Liu, Xue Song, Zhi Zhao, Wei Du, Ying-Chun Chen
Summary: In this study, we found that dienones generated from the Morita-Baylis-Hillman carbonates of 2-cyclopentenone under Pd(0) catalysis could be umpolunged through pi-Lewis base activation to form regioselective eta 2-Pd(0) complexes, which then underwent asymmetric inverse-electron-demand oxa-Diels-Alder reaction with alpha-cyano chalcones. This study successfully constructed a range of fused pyran frameworks with dense substitutions and demonstrated excellent stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Deyang Liu, Zelong Zhang, Jiang Yu, Haihong Chen, Xuan Lin, Ming Li, Lirong Wen, Weisi Guo
Summary: In this study, a direct synthesis method for thiocyanate derivatives was developed using a site-selective benzylic C-H thiocyanation reaction. The reaction exhibited a broad substrate scope and unique selectivity for the benzylic C-H site (2 degrees > 3 degrees > 1 degree) compared to existing methods. Preliminary mechanistic studies suggested a radical-polar crossover process. Additionally, this method was successfully applied for follow-up transformations and late-stage thiocyanation of bioactive molecules.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Mingda Li, Yangbin Jin, Yupeng Chen, Wanqing Wu, Huanfeng Jiang
Summary: This paper reports a new catalytic system for the efficient oxidative amination of unactivated olefins with primary aliphatic amines, leading to the formation of secondary allylic amines. The reaction proceeds through allylic C(sp3)-H activation and nucleophilic amination. The utility of this method is demonstrated in the late-stage modification and streamlined synthesis of drug molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Environmental Sciences
Ji Won Heo, Liangliang An, Jiansong Chen, Jin Ho Bae, Yong Sik Kim
Summary: Research on low-cost bio-adsorbents for the removal of harmful substances from effluents has gained significant attention. This study prepared three types of amino-silane-modified lignins and investigated their adsorption behavior towards cationic and anionic dyes. The results showed that the amino-silane reagents resulted in different molecular self-assembly structures on the lignin surface. The ASLs exhibited excellent adsorption capacities and selectivity based on the pH conditions.
Article
Chemistry, Organic
Rahul Yadav, Darakshan, Tasneem Parvin
Summary: In this study, a one-pot green method for the synthesis of quinoline tethered alpha-amino ketones was reported. The advantages of this method include its environmentally benign process, short reaction time, readily available starting materials, easy purification process, and high yields of the products.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xingben Wang, Frederic W. Patureau
Summary: The highly selective synthesis of mono- and di-2-fluoroallylic amines from gem-difluorocyclopropanes and primary anilines using a Pd catalyst is described. Initial kinetic studies suggest a first order reaction with the gem-difluorocyclopropane substrate and a zeroth order reaction with the aniline coupling partner. The newly synthesized fluoroallylic motifs have important applications in synthetic and medicinal chemistry, and can potentially stimulate the development of coupling methods using strained cyclic building blocks.
CHEMICAL COMMUNICATIONS
(2023)
Article
Nanoscience & Nanotechnology
Lei Gan, Eduardo Andres-Garcia, Guillermo Minguez Espallargas, Jose Giner Planas
Summary: We demonstrate that the carborane-based metal-organic framework (MOF), mCB-MOF-1, exhibits high adsorptive selectivity for CO2:N2 mixtures. This hydrophobic MOF with open metal sites shows exceptional CO2 adsorption capacity and sustained selectivity values even in extremely humid conditions. A comparison with MOF-74(Ni) highlights the superior performance of mCB-MOF-1 under challenging moisture operation conditions.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Oncology
Annette G. Beck-Sickinger, Daniel P. Becker, Oksana Chepurna, Bhaskar Das, Sebastian Flieger, Evamarie Hey-Hawkins, Narayan Hosmane, Satish S. Jalisatgi, Hiroyuki Nakamura, Rameshwar Patil, Maria da Graca H. Vicente, Clara Vinas
Summary: This article summarizes current research on the development of boron delivery drugs for boron neutron capture therapy, which were presented and discussed at the National Cancer Institute (NCI) Workshop on Neutron Capture Therapy held on April 20-22, 2022. The most commonly used boron sources are icosahedral boron clusters attached to various molecules such as peptides, proteins, porphyrin derivatives, dendrimers, polymers, and nanoparticles, as well as encapsulated into liposomes. These boron clusters and/or carriers can be labeled with contrast agents, allowing for imaging techniques like PET, SPECT, and fluorescence to quantify tumor-localized boron and serve as theranostic agents.
CANCER BIOTHERAPY AND RADIOPHARMACEUTICALS
(2023)
Article
Chemistry, Multidisciplinary
Emma Alcock, Pamela Mackey, Aneta Turlik, Khushi Bhatt, Mark E. Light, Kendall N. Houk, Gerard P. McGlacken
Summary: In this study, a highly diastereoselective method was developed to synthesize acyclic 3-amino-1,5-diol derivatives using a tandem double-aldol-Tishchenko reaction. The reaction achieved high diastereoselectivity (dr up to >99 : 1) using a butanone derived sulfinylimine. The reaction also showed regioselectivity and could be applied to challenging cyclobutanone and 3-pentanone derivatives, although with modest diastereomeric ratios.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Claudio Mendicute-Fierro, Paul D. Smith, Mark E. Light
Summary: In this study, a dicompartmental macrocyclic complex, [Ni2(L1)](DMF)2(BPh4)2, was prepared by reacting [Ni(tn)3]Cl2 with 2,6-diformyl-4-methylphenyl disulfide in methanol and in the presence of NaBPh4. The reaction involved a solvent assisted reduction of the disulfide bond and formation of two thiolate ligands. The crystal structure of the complex revealed a binuclear Ni2S2 core bridged by two thiolates within a macrocyclic framework.
Article
Chemistry, Multidisciplinary
Lei Gan, Makenzie T. Nord, Jacob M. Lessard, Noah Q. Tufts, Arunraj Chidambaram, Mark E. Light, Hongliang Huang, Eduardo Solano, Julio Fraile, Fabian Suarez-Garcia, Clara Vinas, Francesc Teixidor, Kyriakos C. Stylianou, Jose G. Planas
Summary: The removal of organophosphorus (OP) herbicides from water has been studied using various methods such as adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. In this study, a Zr-based metal-organic framework (mCB-MOF-2) was used for the adsorption and photodegradation of the OP herbicide glyphosate (GP). The mCB-MOF-2 demonstrated a high adsorption capacity for GP and selectively converted it to non-toxic sarcosine and orthophosphate under UV-vis light irradiation. These findings suggest that mCB-MOF-2 is a promising material for removing OP herbicides from water.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Esther Matamoros, Mark E. Light, Pedro Cintas, Juan C. Palacios
Summary: This paper investigates the formation of Schiff bases and 1,3-oxazolidines derived from salicylaldehydes and a conformationally restricted amino alcohol. The study provides experimental evidence, including crystallographic analyses and DFT-based calculations, on imine/enamine tautomerism. The mechanistic studies reveal the prevalence of imines under thermodynamic control and the formation of 2,4-trans-oxazolidines under acylating conditions.
Article
Nanoscience & Nanotechnology
Nikolaos Aspiotis, Katrina Morgan, Benjamin Maerz, Knut Mueller-Caspary, Martin Ebert, Ed Weatherby, Mark E. Light, Chung-Che Huang, Daniel W. Hewak, Sayani Majumdar, Ioannis Zeimpekis
Summary: This work demonstrates a scalable process for producing large area atomically thin 2D semiconductors with uniform performance. The new atomic layer deposition (ALD) and conversion technique allows for independent control of layer thickness, stoichiometry, and crystallinity. Field effect transistors (FETs) fabricated using this process exhibit high field effect mobility, low subthreshold slope, and high on/off ratios. Additionally, non-volatile memory transistors using ferroelectric FETs (FeFETs) with multiple state switching and a wide memory window are demonstrated, showing the applicability of the process to flexible neuromorphic applications.
NPJ 2D MATERIALS AND APPLICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhen Li, Xiao-Bao Li, Mark E. Light, Anna E. Carrillo, Ana Arauzo, Manuel Valvidares, Claudio Roscini, Francesc Teixidor, Clara Vinas, Felipe Gandara, Elena Bartolome, Jose Giner Planas
Summary: This work demonstrates the successful synthesis of a multi-metallic MTV RE MOF incorporating two, four, six, or eight different RE ions without any compositional segregation. The incorporation of all RE cations is characterized via compositional and structural characterization. The more complex MTV MOF, including all eight RE ions, is characterized using optical, thermal, and magnetic techniques.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Juan Garcia de la Concepcion, Mirian Flores-Jimenez, Louis A. Cuccia, Mark E. Light, Cristobal Viedma, Pedro Cintas
Summary: This paper documents and reinvestigates the solid-state and crystal structures of 4,4'-azobis-4-cyanopentanoic acid (ACPA), a water-soluble azobis-nitrile of immense utility as a radical initiator in living polymerizations and a labile mechanophore that can be embedded within long polymer chains to undergo selective scission under mechanical activation. The X-ray crystal structures of all stereoisomers of ACPA have been reported for the first time, along with further details on enantiodiscrimination and the aggregation behavior of ACPA enantiomers.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Organic
Mark Power, Katrina Mackey, Mark E. Light, David J. Jones, Gerard P. Mcglacken
Summary: Dibenzofuran and its derivatives are important medicinal and natural products, but their synthesis is challenging. This study reports a new C-H functionalization method that works with electron-rich arenes, using tetrabutylammonium acetate as the catalyst, achieving efficient synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ibrahim Assaf, Zhao Zhang, Franco Otaola, Mikel Leturia, Denis Luart, Vincent Terrasson, Erwann Gu
Summary: This research proposes a simple and scalable continuous-flow mode for the green preparation of stable alkali lignin nanoparticles (LNPs) assisted by ultrasound. Spheroid nanoparticles with an average size of 97.2 nm were obtained under the optimized conditions, exhibiting improved stability and UV-blocking properties. The continuous flow mode enables the large-scale production and application of LNPs, offering significant opportunities for industrial production.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2023)
Article
Chemistry, Multidisciplinary
Zhao Zhang, Arnaud Besserer, Christophe Rose, Nicolas Brosse, Vincent Terrasson, Erwann Guenin
Summary: Palladium (Pd) nanoparticles were synthesized in aqueous solution and immobilized in beech wood blocks as Pd@wood catalysts. The wood blocks were treated to improve their internal structure and provide attachment sites for the Pd nanoparticles. The catalytic performance of the Pd@wood catalyst was investigated and showed high activity in two model reactions. Furthermore, the integration of Pd nanoparticles into wood blocks by microwave-assisted synthesis is an effective method for wood functionalization, benefiting metal nanoparticle catalysis in fine chemical synthesis and industrial wastewater treatment.
Article
Chemistry, Physical
Daniel J. M. Irving, Mark E. Light, Matilda P. Rhodes, Terence Threlfall, Thomas F. Headen
Summary: Through X-ray and neutron total scattering, as well as Empirical Potential Structure Refinement (EPSR), the prenucleation structures of saturated aqueous magnesium sulfate are explored. The provided atomistic model reveals isolated octahedral aquo magnesium species, magnesium sulfate pairs, and extended clusters built from corner-sharing MgO6 and SO4 polyhedra. The average first solvation shell of the sulfate anion exhibits a complex and flexible environment, with water molecules brought into proximity by a coordinated hydrated magnesium. Ions' tendency to aggregate into clusters allows for differences in structure between bulk water and pure water.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
