Article
Chemistry, Organic
Hiroki Murakami, Ayano Yamada, Kenichi Michigami, Yoshiji Takemoto
Summary: A novel method has been developed in this study for controlling carbonyl alpha-chirality and functionalizing beta-position through the conjugate addition-asymmetric protonation (CAAP) of alpha,beta-unsaturated carboxylic acids using chiral thiourea-amino boronic acid hybrid catalysts. This method is also applied in the asymmetric synthesis of biologically active compounds.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Mina Rajabi, Jaydee Cabral, Sarah Saunderson, M. Azam Ali
Summary: Chitooligosaccharide (COS), an emerging material carbohydrate polymer, was prepared using a microwave-assisted process. The COS was then used to synthesize COS-poly(ethylene glycol) diacrylate (PEGDA) derivatives through aza-Michael addition. The resulting COS-PEGDA hydrogels showed high biocompatibility and can be potentially used in biomedical applications.
CARBOHYDRATE POLYMERS
(2022)
Article
Chemistry, Physical
Fangfang Guo, Jiean Chen, Yong Huang
Summary: Recently, chiral N-heterocyclic carbenes (NHCs) have been established as powerful catalysts for enantioselective bond-forming processes via noncovalent interactions. A bifunctional NHC with an embedded hydrogen-bonding motif has been reported in this study, showing remarkable tolerance of various Michael acceptors in an asymmetric aza-conjugate addition reaction, with catalytic efficiency far exceeding that of the benchmark tertiary amine-thiourea scaffold.
Article
Chemistry, Applied
Fushuai Li, Zhihong Yang, Yanyan Yang, Qiuhong Huang, Xuling Chen, Pengfei Li, Mingxin Dong, Wenjun Li
Summary: A chiral phosphorus acid catalyzed enantioselective 1,4-conjugate addition of arylamines to in situ formed 7-methylene-7H-indoles from 7-indolylmethanols has been successfully developed for the first time without the use of additives. The catalytic protocol enables the formation of 1,4-adducts with a nitrogen-containing tertiary carbon stereocenter in moderate to high yields and good enantioselectivity under mild reaction conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Zhao-Fei Zhang, Zhong-Hua Gao, Chun-Lin Zhang, Song Ye
Summary: The intramolecular aza-Michael addition of alkyl amines to α,β-unsaturated carboxylic acids catalyzed by N-heterocyclic carbenes has been successfully achieved, allowing for the synthesis of pyrrolidine and piperidine derivatives. The use of chiral NHC catalysts demonstrated promising enantioselectivities up to 55% ee. Further chemical transformations of the products provided carboxylic acids, alcohols, and unprotected amines.
Article
Chemistry, Organic
Stefano Barranco, Federico Cuccu, Dayi Liu, Sylvie Robin, Regis Guillot, Francesco Secci, Valerie Brenner, Michel Mons, Pierluigi Caboni, David J. Aitken, Angelo Frongia
Summary: A new method for the stereoselective one-pot double derivatization of cyclobutene-1-carboxylic acid has been developed. This method involves a mild organic base catalyzed amidation/aza-Michael addition of benzo[d]oxazol-2(3H)-ones, leading to the formation of novel beta-N-heterocyclic cyclobutane carboximide derivatives with a trans geometry. The carboximide moiety can react smoothly with nucleophiles, providing access to diverse derivatives of trans-beta-N-heterocyclic cyclobutanecarboxylic acid, including peptidomimetic structures.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Applied
Yong-Xing Song, Da-Ming Du
Summary: The aza-Michael addition cascade reaction is an important synthetic method for constructing functionalized C-N bonds, widely used in the synthesis of chiral drugs, intermediates, and natural products. This review highlights recent developments in asymmetric synthesis, including various types of aza-Michael addition triggered cascade reactions, reaction mechanisms, and derivatization experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Alper Yildirim, Ufuk Atmaca, Ertan Sahin, Parham Taslimi, Tugba Taskin-Tok, Murat Celik, Ilhami Gulcin
Summary: This article examines the use of oxazolidinones in various applications such as antibiotics and protein synthesis inhibition. The synthesized compounds were found to have potent inhibitory effects on enzymes such as acetylcholinesterase and carbonic anhydrase. Molecular docking and ADMET analysis were conducted to correlate the experimental data.
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2023)
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, Organic
Ya-Fei Li, Lu-Lu Chen, Ya-Ru Deng, Yan-Ru Fan, Zhen-Yu An, Yu Huang
Summary: In this study, a series of alpha,beta-diamino acid derivatives were synthesized through acetic acid catalytic Aza-Michael additions. The reaction achieved C-N bond formation with good functional group tolerance. Under optimized conditions, desired products were obtained in moderate to good yields under mild conditions.
SYNTHETIC COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Audrey Mauger, Maxime Jarret, Aurelien Tap, Remi Perrin, Regis Guillot, Cyrille Kouklovsky, Vincent Gandon, Guillaume Vincent
Summary: We synthesized highly strained pentacyclic caged framework of mavacuran alkaloids and successfully achieved the concise total synthesis of C-fluorocurine, C-profluorocurine, C-mavacurine, normavacurine, 16-epi-pleiocarpamine and taberdivarine H. A strategy involving late-stage Michael addition and intermolecular 1,4-addition reactions was designed. The first total syntheses of C-profluorocurine and C-fluorocurine were achieved through dihydroxylation of C-mavacurine and a pinacol rearrangement, respectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Rong-Kuan Jiang, Yue Pan, Li-Hua Du, Ling-Yan Zheng, Zhi-Kai Sheng, Shi-Yi Zhang, Hang Lin, Ao-Ying Zhang, Han-Jia Xie, Zhi-Kai Yang, Xi-Ping Luo
Summary: In this study, a methodology was developed for the synthesis of N-substituted benzimidazole derivatives using lipase catalysis in continuous-flow microreactors. By optimizing reaction parameters, a wide range of compounds were efficiently synthesized, demonstrating the potential of microfluidic biocatalysis system for fast synthesis of active drugs.
Article
Chemistry, Organic
Giacomo Mari, Lucia De Crescentini, Gianfranco Favi, Fabio Mantellini, Stefania Santeusanio
Summary: A novel protocol for the efficient synthesis of 1H-imidazo[5,1-c][1,4]oxazines has been developed by combining aza-Michael addition of selected primary amines to 1,2-diaza-1,3-dienes (DDs) with isothiocyanates or isocyanates in a sequential 3-component reaction (3-CR) process, resulting in 2-thiohydantoins and hydantoins with suitably positioned functional groups for chemoselective acid-promoted ring-fused formation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Fabian Scharinger, Matthias Weil, Michael Schnuerch, Katharina Bica-Schroeder
Summary: We introduce a simple method for the synthesis of chiral diazabicycloalkanes in a single reaction step. This method is applicable to a wide range of enals and has high functional group tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Shan-Shan Li, Li-Li Zhao, Min Pan, Na Feng, Jin-Bao Peng, Ai-Jun Ma
Summary: A potassium carbonate promoted tandem oxy-Michael addition/cyclization reaction has been developed for the synthesis of diverse substituted naphthopyrans. The use of readily available and inexpensive potassium carbonate as a promoter offers an efficient and sustainable approach to prepare 2-substituted naphthopyrans.
Review
Chemistry, Multidisciplinary
Raquel P. Herrera, M. Concepcion Gimeno
Summary: Gold coordination chemistry has made significant progress in recent years, with the design of novel ligands being a key factor in the synthesis and knowledge advancement of gold coordination compounds.
Article
Chemistry, Physical
Stephany Zarate-Roldan, Maria Concepcion Gimeno, Raquel P. Herrera
Summary: The formal homogeneous gold-catalyzed A(3)-coupling reaction starting from benzyl alcohols allows for the straightforward synthesis of propargylamines. The highly valuable final products are obtained with very good yields in short reaction times, which is fundamental for pharmaceutical synthesis. The methodology's usefulness and efficiency are successfully compared against the same reaction starting from aldehydes.
Article
Chemistry, Physical
Ali Rayes, Stephany Zarate-Roldan, Irene Ara, Manel Moncer, Necmi Dege, M. Concepcion Gimeno, Brahim Ayed, Raquel P. Herrera
Summary: Two new organic-inorganic salts have been synthesized and characterized by X-ray diffraction and thermal analysis, with crystal packing driven by various non-covalent intermolecular forces and water molecules acting as assistants in hydrates. Additionally, one compound undergoes a thermally-triggered single-crystal-to-single-crystal transformation upon dehydration, forming a supramolecular solid compound, and both salts exhibit outstanding catalytic properties in the acetalization process.
Review
Chemistry, Inorganic & Nuclear
Juan Carlos Perez-Sanchez, Raquel P. Herrera, M. Concepcion Gimeno
Summary: This review explores the recent advancements in the combination of the ferrocene structure with gold-mediated catalysis in the field of organometallic chemistry, discussing the application and potential of ferrocene in gold catalysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Isaac G. Sonsona, Andrea Vicenzi, Marco Guidotti, Giorgiana Denisa Bisag, Mariafrancesca Fochi, Raquel P. Herrera, Luca Bernardi
Summary: The study demonstrates the improved selectivity of an asymmetric aldol reaction by replacing part of the catalyst, and identifies the most suitable reaction conditions. However, these conditions seem to be limited to oxindoles bearing a 3-substituent of funapide.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Sandra Ardevines, Eugenia Marques-Lopez, Raquel P. Herrera
Summary: The development of new enantioselective processes, especially organocatalytic methods, is highly relevant in various fields due to the importance of chiral compounds. Over the past two decades, the field of asymmetric organocatalysis has seen exponential growth, with the discovery of numerous organic reactions and transformations that yield compounds with high reactivity and enantioselectivity. Organocatalysts based on various chemical architectures have provided diverse activation modes for selective synthesis of valuable compounds.
Article
Chemistry, Organic
Guillermo Canudo-Barreras, Daniel Salvador, Raquel P. Herrera, M. Concepcion Gimeno
Summary: This work demonstrates the gold-catalyzed formation of 1,3-thiazine/1,3-thiazinane and the isolation of these tautomers. The developed protocol allows for the efficient synthesis of various 1,3-thiazine derivatives and the generation of different isomers depending on the compound's state. This study has implications for the synthesis of biologically relevant molecules and the understanding of tautomerism.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Christian Ascaso-Alegre, Raquel P. Herrera, Juan Mangas-Sanchez
Summary: The combination of small-molecule catalysis and enzyme catalysis shows great potential in asymmetric synthetic chemistry. The one-pot three-step chemoenzymatic cascade combination described in this study allows for efficient synthesis of chiral nitro alcohols with high overall yields and excellent selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Sandra Ardevines, Eugenia Marques-Lopez, Raquel P. Herrera
Summary: This review summarizes the research on pyrazole derivatives as antitumor agents. Pyrazole, a five-membered aromatic heterocycle ring with two adjacent nitrogen atoms, has been postulated as a potent candidate in the pharmacological context. Due to its presence in many natural substances, pyrazole is an interesting therapeutic target covering a broad spectrum of biological activities, and its potential as antitumor agents has been explored in various investigations, showing promising results in certain cases. Therefore, this review focuses on breast cancer, the leading cause of cancer mortality in women in some countries, and covers a range of research from the earliest studies published in 2003 to the most recent ones in 2021.
CURRENT MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sandra Ardevines, Fernando Auria-Luna, Eduardo Romanos, Vanesa Fernandez-Moreira, Andrea Benedi, M. Concepcion Gimeno, Isabel Marzo, Eugenia Marques-Lopez, Raquel P. Herrera
Summary: 1,4-Dihydropyridine is a privileged scaffold with good anticancer activity. A family of 23 new compounds based on this structure core has been synthesized, and their cytotoxicity and photo-physical properties have been evaluated.
ARABIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Applied
Sandra Ardevines, Devan Horn, Juan Alegre-Requena, Marta Gonzalez-Jimenez, M. Concepcion Gimeno, Eugenia Marques-Lopez, Raquel P. Herrera
Summary: An enantioselective C-P bond formation has been developed by activating C(sp(3))-H in an oxidation step, followed by an organocatalytic hydrophosphonylation protocol. The Pudovik reaction achieved asymmetric organocatalysis using a one-pot strategy with different alcohols and phosphite, MnO2 as the oxidant, and a chiral squaramide as the organocatalyst. The reaction scope produced enantiomerically enriched a-hydroxy phosphonates with yields ranging from 40% to >95% and enantioselectivities from 64% to >99%. Furthermore, this methodology has demonstrated the formation of a tetrasubstituted carbon stereocenter in situ, using diphenyl phosphite, to generate an acetophenone derivative. Therefore, this approach represents an asymmetric strategy for constructing chiral C-P bonds, which is significant for the pharmaceutical industry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Eugenia Marques-Lopez, Isaac G. Sonsona, Miryam Garces-Marin, M. Concepcion Gimeno, Raquel P. Herrera
Summary: In this study, the potential of phosphites as nucleophiles for the asymmetric synthesis of chiral chromene derivatives was explored. By employing asymmetric organocatalyzed phospha-Michael addition, chiral chromenylphosphonates were synthesized using a bifunctional squaramide. The optimized protocol provided good reactivity with yields of up to 95% and chiral products with an enantiomeric excess of up to 98%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Stephany Zarate-Roldan, M. Concepcion Gimeno, Raquel P. Herrera
Summary: A novel approach for allylic alkylation using a variety of allylic alcohols under mild conditions and deep eutectic solvents (DESs) is described. The use of a simple DES mixture of choline chloride (ChCl) and lactic acid has shown excellent results for a wide range of substrates, providing a greener alternative to previously reported methods. This procedure also demonstrates the trapping of allylic carbocations with indole derivatives and the successful use of challenging nucleophiles such as amides, carbamates, azides, and sulfonamides.
Article
Chemistry, Inorganic & Nuclear
Daniel Salvador-Gil, Raquel P. Herrera, M. Concepcion Gimeno
Summary: The reaction between propargylamines and isothiocyanates can selectively produce iminothiazolidines, aminothiazolines, or mixed thiazolidine-thiourea compounds under mild conditions. Secondary propargylamines lead to the formation of cyclic 2-amino-2-thiazoline derivatives, while primary propargylamines form iminothiazoline species. These cyclic thiazoline derivatives can further react with excess isothiocyanate to give rise to thiazolidine-thiourea compounds. Coordination studies of these heterocyclic species towards silver and gold have been conducted, resulting in the synthesis of complexes of different stoichiometries. Preliminary studies on the cytotoxic activity of these ligands and complexes in lung cancer cells show that their coordination to metals, especially silver, significantly enhances the cytotoxic activity.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Juan Carlos Perez-Sanchez, Raquel P. Herrera, M. Concepcion Gimeno
Summary: Gold(II) complexes have been less utilized in catalysis compared to their gold(I) and gold(III) counterparts. However, gold(II) complexes offer potential in homo-coupling and cross-coupling reactions, as they are more easily accessible through simplified oxidation and reduction processes. Gold(II) exhibits characteristics of both soft acid gold(I) and hard acid gold(III). This review explores the unique reactivity and potential applications of gold(II) species, highlighting their significance in catalytic transformations.
DALTON TRANSACTIONS
(2024)