Article
Chemistry, Organic
Marine Pinaud, Leila Vaitilingom, Gayathiri Gnanalingam, Tania Xavier, Erwan Le Gall, Marc Presset
Summary: The use of N-alkyl imines in decarboxylative Mannich reaction with substituted malonic acids half oxyesters (SMAHOs) has been developed to afford a direct access to secondary beta(2,3)-aminoesters. The transformation occurs under very practical conditions (DABCO as a catalyst in bulk toluene and open to air) and can be performed with a broad range of each substrate in yields of 36 to 97 %. Importantly, the reaction was found to require the use of acidic additives in combination with the organocatalyst to limit the competitive olefination reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Marine Pinaud, Emilie Plantiveau, Eric Huet, Erwan Le Gall, Marc Presset
Summary: Mannich-type reactions involving alkylzinc reagents have been developed using different strategies. We found that simple heating allows the addition of these organometallic species to sulfonyl imines, giving Mannich products in moderate to excellent yields (14 examples, 30-99%). Interestingly, N-alkyl imines can also be used as suitable partners after activation as an acyliminium by acetyl chloride (12 examples, 49-86%) or, more originally, by TMSCl (14 examples, 26-87%). These methods are complementary, providing both N-protected secondary or tertiary amines and N-unprotected secondary amines in good yields, with improved eco-compatibility and under simple conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Philip J. Chevis, Chi Bong Eric Chao, Christopher Richardson, Christopher Hyland, Richmond Lee, Stephen G. Pyne
Summary: The crotylation reactions of chiral α-F, α-OBz and α-OH aldehydes were carried out under Petasis-borono-Mannich conditions using (E)- or (Z)-crotylboronates and primary amines. The reactions resulted in γ-addition products with high diastereoselectivity and enantioselectivity. The stereochemical outcomes of the reactions could be explained using transition state models and were supported by DFT calculations. Representative products were transformed into highly functionalized 1,2,3,6-tetrahydropyridines and 3H-oxazolo[3,4-a]pyridine-3-ones, which are valuable scaffolds in synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Huiting Lv, Yongli Du, Haibin Zhang, Yong Zheng, Zhijia Yan, Ning Dong
Summary: Mannich-type reactions utilize active alpha-H compounds, amines, and aldehydes to synthesize valuable beta-aminocarbonyl compounds. The yield, selectivity, and regioselectivity of the reaction are influenced by catalysts and the structural characteristics of the substrates. This article summarizes the developments in symmetric and asymmetric Mannich-type reactions according to the type of substrates and analyzes the factors affecting reaction outcomes.
Article
Chemistry, Physical
Feng Zhong, Wen-Jun Yue, Xing-Hao Yin, Hong-Ming Zhang, Liang Yin
Summary: A copper(I)-catalyzed alkynylogous Mannich-type reaction is developed to provide chiral alpha-allenylamine derivatives in high selectivities. Additionally, a copper(I)-catalyzed cascade cyclization yields chiral beta-lactams containing a pyrazole moiety in high enantioselectivity. The synthetic utility and versatility of the alkynylogous product are demonstrated.
Article
Polymer Science
Fusun Seyma Gungor
Summary: A compound with a phenolic group was successfully synthesized and subjected to Mannich reactions with primary amine compounds and paraformaldehyde, resulting in three thermally polymerizable naphthoxazines with high yields. The structures of the exchange products were characterized using analytical techniques and the ring-opening polymerization behavior was investigated.
EUROPEAN POLYMER JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Hristo Petkov, Svilen P. Simeonov
Summary: Currently, there is growing interest in 1-amidoalkyl-2-naphthol derivatives due to their biological activities and potential use in the synthesis of other important bioactive molecules. One-pot multicomponent Mannich reactions are commonly employed for the synthesis of the 1-amidoalkyl-2-naphthol moiety. This review summarizes recent advances in the preparation of 1-amidoalkyl-2-naphthols using different catalysts and provides an overview of published data from the past 3 years. It also highlights the structure, synthetic transformation, and biological importance of this class of products.
APPLIED SCIENCES-BASEL
(2023)
Article
Chemistry, Organic
Cansu Gulbenek, Muhammet Yildirim, Arzu Yildirim
Summary: In this study, new polysubstituted nitropyridimines were efficiently synthesized through double Mannich cyclizations under microwave irradiation. Some of the nitropyridimines showed moderate to low antioxidant and antibacterial activities.
Review
Chemistry, Organic
Aslihan Ayvaz, Sinem Gorkem Demirbas, Ahmet Demirbas, Neslihan Demirbas
Summary: Due to the increasing environmental pollution and its detrimental impact on the ecosystem, scientists have developed new chemical strategies using eco-friendly chemicals, solvents, catalysts, and alternative energy sources. Deep eutectic solvents (DESs) are low-melting mixtures primarily consisting of quaternary ammonium salt and hydrogen-bond acceptors. DESs have advantages such as low toxicity, easy preparation, low cost, biodegradability, low vapor pressure, and recyclability.
CURRENT ORGANIC CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Minoo Dabiri, Noushin Farajinia Lehi, Reza Mohammadian
Summary: Fluoro-organic compounds have attracted significant interest for their role in developing new bioactive materials and healthcare products. Catalytic Mannich reaction allows for the synthesis of versatile amine synthons, opening clear paths for the synthesis of natural product and pharmaceutical molecules. This review highlights the use of catalytic asymmetric Mannich reactions in the synthesis of fluorine-containing amine compounds and discusses possible distinct mechanisms.
MOLECULAR DIVERSITY
(2022)
Review
Chemistry, Applied
Jaume Rostoll-Berenguer, Gonzalo Blay, Jose R. Pedro, Carlos Vila
Summary: This review summarizes recent publications on asymmetric oxidative Mannich reactions using amines as electrophiles, including the different oxidants used and the scope and limitations of the different catalytic systems.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Wei Liu, Tianren Qin, Wansen Xie, Jinmiao Zhou, Zidan Ye, Xiaoyu Yang
Summary: We have developed an efficient modular asymmetric synthesis of azahelicenes from readily available polycyclic aromatic amines, aldehydes, and (di)enamides, employing a central-to-helical chirality conversion strategy. A series of aza[5]- and aza[4]helicenes bearing various substituents were easily obtained with good yields and high enantioselectivities. The diverse derivatizations and the preliminary application of the azahelicene derivative as a chiral organocatalyst demonstrated the potential of this method, and the photophysical and chiroptical properties of these azahelicenes were well studied, showing potential applications in novel organic optoelectronic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Multidisciplinary Sciences
Yingfu Lin, Rui Zhang, Di Wang, Tim Cernak
Summary: Efficient chemical synthesis is crucial for meeting the future demands of pharmaceuticals, materials, and agrochemicals. While the automation of retrosynthetic analysis for moderately complex molecules has been ongoing for decades, the vast number of possible routes has posed challenges for computer hardware and software until recently. In this study, we introduce a computational strategy that combines computer-aided synthesis planning with molecular graph editing to minimize the synthetic steps needed for producing alkaloids. Through the utilization of high-impact key steps identified in computer-generated retrosynthesis plans using graph edit distances, we have successfully achieved an enantioselective three-step synthesis of (-)-stemoamide.
Article
Chemistry, Physical
Sanghoon Shin, Yuhyun Kim, Sungwoo Hong
Summary: In this study, an innovative Ag(I)-catalyzed carbene transfer reaction using [1.1.1]propellane as a precursor was reported. The method involves the formation of Ag-bound oxonium ions as intermediates through the reaction between the Ag-carbene complex and cyclic ether-type solvents. The subsequent nucleophile-induced C-O bond cleavage leads to a controllable three-component etherification of methylene cyclobutane. The method demonstrates potential for the late-stage functionalization of complex, biologically relevant molecules and synthetic manipulations of the resulting products.
Article
Chemistry, Organic
Justo Cobo, Sebastian Molina, Adolfo Sanchez, Manuel Nogueras, Braulio Insuasty, Fabian Orozco-Lopez
Summary: This study investigated the reactivity of 6-iminophosphoranepyrimidines with DMAD and ethyl propiolate as dienophiles. Pyrimidine derivatives with a viable 2-azadienic moiety can undergo [4+2]/retro-[4+2] and [2+2]/retro-[2+2] reactions, while those without this structure can only undergo [2+2]/retro-[2+2] reactions involving the phosphazene moiety.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2022)
Article
Chemistry, Medicinal
Ivan Diaz, Sofia Salido, Manuel Nogueras, Justo Cobo
Summary: A series of novel pyrimidine-quinolone hybrids were designed and synthesized as inhibitors of lactate dehydrogenase A (hLDHA) using a computer-aided approach. By evaluating the inhibitory activity of different synthesized hybrids, new compounds with promising activity were successfully designed, and a preliminary structure-activity relationship was established.
Article
Biochemistry & Molecular Biology
Lina Fernanda Castano, Jairo Quiroga, Rodrigo Abonia, Daniel Insuasty, Oscar M. Vidal, Rosalia Sena, Vivian Rubio, Gloria Puerto, Manuel Nogueras, Justo Cobo, Juan Guzman, Alberto Insuasty, Braulio Insuasty
Summary: A series of sulfonamides and chalcone-sulfonamide hybrids were synthesized and evaluated for their anticancer and antituberculosis activities. Some of the compounds showed potential activity against cancer and tuberculosis, but further optimization is needed.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Juan -Carlos Castillo, Jose J. Martinez, Diana Becerra, Hugo Rojas, Mario A. Macias
Summary: In this study, the catalyst-free synthesis of (5-formylfuran-2-yl)methyl 4-chlorobenzoate was achieved by an O-acylation reaction of 5-hydroxymethylfurfural with 4-chlorobenzoyl chloride using a slight excess of triethylamine in dichloromethane. The structure of the compound was characterized by various spectroscopic techniques and it was found to crystallize in a Sohncke P212121 space group, indicating its potential nonlinear optic property.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Sonia Mancipe, Juan-Carlos Castillo, Maria H. Brijaldo, Viviana P. Lopez, Hugo Rojas, Mario A. Macias, Jaime Portilla, Gustavo P. Romanelli, Jose J. Martinez, Rafael Luque
Summary: This study describes the use of boric acid deposited on hydrotalcite as a catalyst for the Knoevenagel reaction between HMF derivatives and active methylene compounds. The catalyst showed high activity, good selectivity, and could be reused multiple times without significant loss of activity.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Angelica Salinas-Torres, Elizabeth Jimenez, Diana Becerra, Jose J. Martinez, Hugo Rojas, Juan-Carlos Castillo, Mario A. Macias
Summary: In this study, the 2-oxo-2H-chromen-7-yl 4-chlorobenzoate (compound 3) was synthesized with high yield using an O-acylation reaction. The structure of compound 3 was fully characterized, and its crystal structure was determined to be monoclinic. The packing of compound 3 in the crystal structure was mainly controlled by C-H···O hydrogen bonds, but C-H···Cl interactions were also important. Compound 3 showed low activity against several cancer cell lines. These findings are significant for crystal engineering and non-linear optics.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Physical
Omar Portilla-Zuniga, Oscar M. Bautista-Aguilera, Jose J. Martinez, Hugo Rojas, Mario A. Macias, Isabel Iriepa, Adrian Perez-Redondo, Angel Sathicq, Juan-Carlos Castillo, Gustavo P. Romanelli
Summary: The Paal-Knorr reaction of acetonylacetone with primary amines catalyzed by CATAPAL 200 under conventional heating at 60 degrees C for 45 min resulted in N-substituted pyrroles in yields of 68-97%. CATAPAL 200, with its high percentage of Bronsted-Lewis acid sites (23%) and pore diameter (37.8 nm), promotes the formation of pyrrole ring by facilitating condensation and dehydration processes. This protocol offers simplicity, high yields, reduced reaction time, solvent-free conditions, stoichiometric amounts of reactants, low catalyst loading, and clean reaction profile. Furthermore, CATAPAL 200 is inexpensive and readily available, making it a cost-effective option for chemical transformations. The catalyst can be reused for up to five cycles without significant loss of catalytic activity, making this protocol sustainable and advantageous compared to conventional methods.
Article
Chemistry, Multidisciplinary
Diana R. Vera, Diana M. Ardila, Alirio Palma, Justo Cobo, Christopher Glidewell
Summary: Four new 2,4-distyrylquinolines and one 2-styryl-4-[2-(thiophen-2-yl)vinyl]quinoline have been synthesized and characterized. Different orientations of the styryl units in relation to the quinoline nucleus were observed. The structure of the compounds was analyzed and compared with related compounds.
ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY
(2023)
Article
Crystallography
Juan-Carlos Castillo, Diana Becerra, Mario A. A. Macias
Summary: We reported a time-efficient synthesis of quinolin-8-yl 4-chlorobenzoate (3) through an O-acylation reaction between 8-hydroxyquinoline (1) and 4-chlorobenzoyl chloride (2) mediated by triethylamine. The reaction was conducted in acetonitrile at 80 degrees C for 20 minutes in the Monowave 50 reactor. Compound 3 was fully characterized using various analytical techniques, and its crystal structure exhibited unique C-H···N, C-H···O, Cl···π, and π···π interactions.
Article
Chemistry, Organic
Diana Becerra, Hugo Rojas, Juan-Carlos Castillo
Summary: The 2-oxo-1,2-dihydroquinolin-8-yl 4-chlorobenzoate was synthesized efficiently through an O-acylation reaction mediated by triethylamine between 8-hydroxyquinolin-2(1H)-one and 4-chlorobenzoyl chloride in acetonitrile at room temperature. This method offers a clean reaction pathway and a straightforward procedure. The synthesized 2-oxoquinoline derivative was characterized using spectroscopic, spectrometric, and thermal analyses for understanding its molecular structure and thermal properties comprehensively.
Article
Chemistry, Multidisciplinary
Valeria Palermo, Jhoan M. Camargo Lopez, Maria H. Brijaldo, Sergio Acevedo, Sonia Mancipe, Juan-Carlos Castillo, Hugo A. Rojas, Fabio B. Passos, Jose J. Martinez, Gustavo P. Romanelli
Summary: Conversion of fruit seed residual biomass into biochar using MgCl2 as an activating agent and applying it as an acidic-basic catalyst has shown high selectivity.
Article
Chemistry, Multidisciplinary
Erika Moreno-Suarez, Rafael Avila-Acosta, Karen Sanchez-Ramirez, Juan-Carlos Castillo, Mario A. Macias
Summary: A new pyrrole-pyrazole derivative, C16H16BrN3, was synthesized through a citric acid-catalyzed Paal-Knorr reaction. The synthetic protocol utilized stoichiometric amounts of reactants, an ecofriendly solvent, and a cost-effective, non-toxic, and biodegradable organocatalyst. Spectroscopic, thermal, and X-ray crystallographic analyses provided a comprehensive understanding of the molecular structure.
ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY
(2023)
Review
Chemistry, Medicinal
Lizeth Arce-Ramos, Juan-Carlos Castillo, Diana Becerra
Summary: This review provides an overview of the synthesis and exhaustive biological studies conducted on benzo[b]furan derivatives, highlighting their potential as anticancer, antibacterial, and antifungal agents, as well as their applications in drug discovery and medicinal chemistry.
Article
Chemistry, Multidisciplinary
Sonia Mancipe, Valentina Coca, Juan-Carlos Castillo, Hugo Rojas, Maria Helena Brijaldo, Claudia Castaneda, Jose Jobanny Martinez, Gustavo Pablo Romanelli
Summary: In this study, the catalytic activity of Mg(OH)(2) and MgO materials were investigated, along with the reaction between HMF and malononitrile under solvent-free conditions. The combination of synthesis methods were found to affect the properties of the catalysts, and water played a crucial role in achieving high yields. High yields near 90% were achieved using a simple and inexpensive method.
COMPTES RENDUS CHIMIE
(2023)
Article
Chemistry, Physical
Diana Becerra, Jaime Portilla, Hugo Rojas, Mario A. Macias, Juan-Carlos Castillo
Summary: A regioselective synthesis of two 1-(arylsulfonyl)-1H-1,2,4-triazol-5-amines was described, and the resulting compounds were characterized by various techniques. The compounds exhibited unique molecular structures and packing arrangements. In vitro experiments showed that they possessed promising anticancer activity.
JOURNAL OF MOLECULAR STRUCTURE
(2024)
