Article
Chemistry, Organic
Xiangjie Chen, Yi An, Guangfen Du, Yujie Zhao, Lin He, Jixing Zhao, Shi-Wu Li
Summary: This study established a method for asymmetric catalytic vinylogous Michael addition of 2-methyl-3,5-dinitrobenzoates to unsaturated ketones using chiral rhodium catalysts. This strategy successfully synthesized a variety of optically pure compounds containing imidazole and 3,5-dinitrobenzene skeletons.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Hao Fu, Linbo Gong, Shuling Gong
Summary: In this study, a self-dispersible, non-ionic waterborne comb-like polyester (NWCPE) was successfully synthesized by grafting an amino-terminated hydrophilic polyether to a series of linear polyesters using a facile and mild aza-Michael addition. The NWCPE dispersion showed excellent storage stability and hydrolysis resistance, and the cross-linked film exhibited good water resistance and mechanical properties.
Article
Chemistry, Multidisciplinary
Yuki Yamamoto, Akiya Ogawa
Summary: Transition-metal-catalyzed addition of organosulfur compounds to carbon-carbon unsaturated bonds is an important synthetic method. However, the presence of organic sulfur compounds as catalyst poisons has limited the development of related reactions. Recent research has focused on novel systems to suppress the catalyst poisons.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Physical
Dou Ma, Xin Huang, Yu Zhang, Lu Wang, Bo Wang
Summary: Metal-organic frameworks (MOFs) have shown great potential in various applications. More than 20,000 MOFs have been reported, most of which are synthesized using hydrothermal or solvothermal methods. However, these methods have limitations in terms of harsh synthesis conditions and difficulty in scale-up. This review aims to understand the crystallization mechanisms of MOFs, explore large scale synthesis routes, and discuss the prospects of MOF shaping and processing for industrial application.
Review
Chemistry, Physical
Dou Ma, Xin Huang, Yu Zhang, Lu Wang, Bo Wang
Summary: Metal-organic frameworks (MOFs) are constructed by metal ions or clusters with organic ligands and have shown great potential in various applications. Over 20,000 MOFs have been reported through adjusting composition and reaction conditions, mostly synthesized by hydrothermal or solvothermal methods. However, the harsh synthesis conditions and difficulty in scale-up limit their industrial production and application. This review explores the crystallization mechanisms of MOFs, promising synthetic routes for large scale synthesis, and prospects of MOF shaping and processing for industrial application.
Article
Chemistry, Physical
Schirin Hanf, Carlos Lizandara-Pueyo, Timo Philipp Emmert, Ivana Jevtovikj, Roger Glaeser, Stephan Andreas Schunk
Summary: Metal alkoxides are important precursors for functional materials, but their poor solubility in organic solvents limits their application in sol-gel processes. In this study, we propose three different solubilization strategies for metal alkoxides, including derivatization, hetero-metallization, and CO2 insertion. The CO2 insertion strategy allows for the formation of metal alkyl carbonates, which can be effectively used in sol-gel chemistry to synthesize crystalline carbonates and hydroxycarbonates with controlled hydrolysis. The synthesized Cu/Zn-based catalysts showed comparable catalytic activity to commercial standard reference catalysts for methanol synthesis.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Physical
Catherine P. Raptopoulou
Summary: Metal-organic frameworks (MOFs) are porous materials constructed from metal ions or oligonuclear metallic complexes and organic ligands. They exhibit high porosity, large specific surface area, and high thermal stability. These materials have potential applications in environment, energy, and biomedicine, as well as being useful as catalysts, sensors, and various functional materials.
Article
Chemistry, Multidisciplinary
Lewis R. Thomas-Hargreaves, Chantsalmaa Berthold, William Augustinov, Matthias Mueller, Sergei I. Ivlev, Magnus R. Buchner
Summary: In this study, diphenylberyllium is found to react cleanly with various protic compounds. The long-postulated structures of beryllium compounds have been verified and their behavior differences have been examined. Additionally, a beryllium Grignard reagent with a non-bulky aryl group has been prepared.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Pedro de Jesus Cruz, William R. Cassels, Chun-Hsing Chen, Jeffrey S. Johnson
Summary: This study reports the discovery and development of a new synthetic method that allows simultaneous control over multiple stereogenic centers for efficient preparation of pharmaceutical compounds. By merging asymmetric Michael addition and crystallization-induced diastereomer transformation, useful compounds with three contiguous stereogenic centers have been successfully synthesized.
Article
Chemistry, Organic
Sadhanendu Samanta, Jin Cui, Hidetoshi Noda, Takumi Watanabe, Masakatsu Shibasaki
Summary: In this study, a gram-scale syn-selective asymmetric vinylogous addition of butenolides to chromones was developed using an Al-Li-BINOL (ALB) complex catalyst. The reaction showed high diastereoselectivity with ratios up to 20:1 and enantioselectivity of 84-98% for various substrate combinations. This method is complementary to previous reports and improves selectivity for several chromones. Computational studies support the role of ALB as a bifunctional catalyst in this reaction and provide insights into the origin of the observed stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sadhanendu Samanta, Jin Cui, Hidetoshi Noda, Takumi Watanabe, Masakatsu Shibasaki
Summary: A gram-scale syn-selective asymmetric vinylogous addition of butenolides to chromones, catalyzed by an Al-Li-BINOL (ALB) complex, was developed in this study. The diastereoselectivity reached 20:1 with 84-98% ee for various combinations of substrates. This protocol complements previous methods and improves selectivity for multiple chromones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Miao Zeng, Jing-Wen Xue, Hongwu Jiang, Kaiwen Li, Yunong Chen, Zhuqi Chen, Guochuan Yin
Summary: Effective organic synthesis protocols are crucial for pharmaceutical developments. A Pd(II)/LA-catalyzed decarboxylative addition reaction was introduced for the synthesis of bis(indolyl)-methane derivatives with moderate to good yields. The catalytic efficiency was highly dependent on the Lewis acidity, showing good tolerance towards different substituents on the indole skeleton and benzyl ring of propiolic acids.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Witsanu Sombat, Panassilp Authai, Panuwat Padungros, Voravee P. Hoven
Summary: Micellar systems have been recognized as effective nanoreactors for performing chemical reactions in aqueous solutions. This research developed nanoreactors from polymeric micelles, in which organic substrates were encapsulated and stabilized. The micellar nanoparticles assembled from PBAM-ran-PHPAM were spherical and well-dispersed in water, with a diameter of less than 170 nm. Thia-Michael addition reactions in the presence of the PBAM26-ran-PHPAM copolymer resulted in high conversions and isolated yields of the Michael adducts. The micellar nanoreactors were also reusable up to 10 times with a high reaction conversion of 75%.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Toshimichi Ohmura, Yuta Takaoka, Michinori Suginome
Summary: The copper-catalyzed silafunctionalization of alkynes using silylboronic ester as a silicon source has made rapid progress. The trans-selective 1,2-addition of silylboronic esters to internal arylalkynes was efficiently promoted by the CuOt-Bu/RCy2P/NaOt-Bu catalysts, with a stereochemical switch to cis-addition observed in reactions utilizing Me-2(i-PrO)Si-B(pin) in hydrocarbon solvents including cyclohexane.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ricardo Rodriguez, Marina Sicignano, Jose Aleman
Summary: In this study, a convenient strategy using gem-difluorinated sulfinates as upgrading-masks is reported, which allows the decomposition of precursors into corresponding alkyl radicals. The stereocontrolled light-driven insertion of gem-difluoro derivatives into unsaturated aldehydes is achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Miguel A. Valle-Amores, Ana M. Martinez-Gualda, Leyre Marzo, Alberto Fraile, Jose Aleman
Summary: A visible-light mediated strategy for the synthesis of cyclic beta-amino carbonyl derivatives with three contiguous stereogenic centers is introduced. The reactivity of the transformation relies on the substrate-catalyst complex to assist both enantioselectivity control and photoredox reactions. This transformation enables an enantioselective [3 + 2] photocycloaddition between coordinated alpha,beta-unsaturated acyl imidazoles and cyclopropylamine derivatives.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Miguel A. Valle-Amores, Matias Blanco, Stefano Agnoli, Alberto Fraile, Jose Aleman
Summary: This article presents a carbocatalytic synthesis method using mild-oxidized multiwalled carbon nanotubes catalyst as a carrier to achieve a smooth condensation reaction between aldehydes and hydrazine, resulting in the formation of azines. The method shows excellent yields and selectivity for aromatic substrates, with potential applications in nonlinear optics, organic materials, and biological active compounds crafting.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Andrzej Nowok, Wioleta Cieslik, Mateusz Dulski, Karolina Jurkiewicz, Joanna Grelska, Jose Aleman, Robert Musiol, Anna Z. Szeremeta, Sebastian Pawlus
Summary: This article uses a combination of quantum computations and various studies to analyze the nature of atypical bifurcated hydrogen bonds (BHBs). The experiments prove that self-organization through BHBs is prevalent in H-bonding systems, even with high screening of proton-donor and proton-acceptor groups. It is also shown that even highly sterically hindered Schiff bases can form lasting centrosymmetric dimers through BHBs. The driving force for their ordering tendency is the disorder in the molecular scaffold.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Green & Sustainable Science & Technology
Alberto Lopez-Magano, Ruben Mas-Balleste, Jose Aleman
Summary: The study demonstrated the stable coordination of palladium centers by the phenanthroline unit in Phen-COF, leading to enhanced catalytic activities and recyclability. The concept of isolating and immobilizing catalytic sites in Pd@Phen-COF significantly improved catalytic outputs compared to analogous molecular catalysts, particularly in C-C cross-coupling reactions.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Pharmacology & Pharmacy
Tugce Boztepe, Sebastian Scioli-Montoto, Rocio C. Gambaro, Maria Esperanza Ruiz, Silvia Cabrera, Jose Aleman, German A. Islan, Guillermo R. Castro, Ignacio E. Leon
Summary: Colorectal cancer, the second leading cause of cancer death, is referred to as colon or rectal cancer depending on the site of formation. The platinum-based compound 8-QO-Pt has shown promising anticancer activity. In this study, three different systems of 8-QO-Pt-encapsulated nanostructured lipid carriers (NLCs) with riboflavin (RFV) were investigated. The results demonstrated the higher cytotoxicity of the 8-QO-Pt-loaded NLC/RFV formulations compared to free 8-QO-Pt, indicating the potential of RFV-targeted NLC systems for colon cancer treatment.
Review
Chemistry, Applied
Noelia Salaverri, Jose Aleman, Leyre Marzo
Summary: In 1962, Paul J. de Mayo discovered the photochemical reaction involving 1,3-diketones and double bonds, leading to the formation of 1,5-diketones. Since then, this reaction has been widely used for the synthesis of various natural products. It has been applied to different carbonyl systems and unsaturated systems, and recent advances in photocatalytic conditions have been made. This review article provides a comprehensive overview of the classical de Mayo reaction and focuses on its scope, potential, regioselectivity, and reaction mechanism in the context of photocatalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Roberto del Rio-Rodriguez, Jose A. Fernandez-Salas, Jose Aleman
Summary: This work presents an electrochemical method for synthesizing allyl sulfones by sulfonating allyl trifluoroborates. The process involves a radical addition to the alkene and subsequent elimination of the trifluoroborate moiety, leading to the formation of substituted allyl sulfones. The reaction is highly efficient and versatile, compatible with various aromatic, heteroaromatic, and aliphatic systems. It offers a cost-effective and environmentally friendly approach for synthesizing recognizable organic motifs in both synthetic and medicinal chemistry.
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Roberto del Rio-Rodriguez, Jose A. Fernandez-Salas, Jose Aleman
Summary: This work describes the electrochemical synthesis of allyl sulfones via sulfonation of allyl trifluoroborates. The process is efficient and versatile, and does not require a mediator or additional supportive electrolyte, making it a cost-effective, safe, and environmentally friendly method for synthesizing this recognizable organic motif. The high selectivity of the sulfonation reaction is attributed to the stability of the electrochemically-generated intermediate carbocation.
Article
Chemistry, Organic
Miguel A. Valle-Amores, Claudia Feberero, Ana Martin-Somer, Sergio Diaz-Tendero, Andrew D. Smith, Alberto Fraile, Jose Aleman
Summary: In this study, a highly enantioselective organocatalyzed [3 + 2] cycloaddition reaction between furanone derivatives and azomethine ylides was presented. The success of this reaction is attributed to intramolecular hydrogen bond activation and the formation of highly multifunctional bicyclic adducts with five stereogenic centers. The reaction also achieved a highly efficient kinetic resolution of butenolides, leading to the formation of furan-2(5H)-ones and furo[3,4-c]pyrrolidinones with high enantioselectivities. Quantum chemistry calculations revealed the crucial role of hydrogen bonding in promoting facial discrimination and achieving a highly selective kinetic resolution.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Lorena Fragoso-Jarillo, Alberto F. Garrido-Castro, M. Carmen Maestro, Jose A. Fernandez-Salas, Jose Aleman
Summary: We report a general, facile, and environmentally friendly electrochemical method for the Minisci-type alkylation of N-heteroarenes using widely available alkyl halides as radical precursors. The method efficiently generates primary, secondary, and tertiary alkyl radicals, which can be coupled with a variety of N-heteroarenes. The method demonstrates high functional group tolerance and has been applied in the synthesis of biologically valuable building blocks.
Article
Chemistry, Multidisciplinary
Jose Luis Nova-Fernandez, Montana J. Garcia, Leonardo Mollari, Gustavo Pascual-Coca, Silvia Cabrera, Jose Aleman
Summary: A sustainable strategy for alkylation of heterocycles is proposed, which involves the in situ generation and further in-line use of alkyl zinc sulfinates through a continuous-flow system. The protocol demonstrates environmentally friendly characteristics by employing a green solvent mixture, a metal-free oxidant, and low waste generation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Andrea Guerrero-Corella, Alberto Fraile, Jose Aleman
Summary: The activation of molecules through intramolecular hydrogen-bond formation is an effective strategy in organic synthesis for enhancing reactivity, stabilizing chemical species, and controlling enantioselectivity.
ACS ORGANIC & INORGANIC AU
(2022)
