Review
Chemistry, Organic
Gillian McArthur, Steven Abel, Giulio Volpin, David M. Barber
Summary: This review summarizes the methods and importance of enantioselective synthesis of 2-isoxazolines and 2-isoxazolin-5-ones with fully substituted stereocenters, as well as discusses the limitations and future developments in this research field.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ramasamy Jayarajan, Tautvydas Kireilis, Lars Eriksson, Kalman J. Szabo
Summary: In this study, a variety of aliphatic, aromatic, and heterocyclic boronic acids were successfully modified using trifluorodiazoethane and BINOL derivatives, resulting in the synthesis of chiral trifluoromethyl containing boronic acid derivatives. The conversion of the chiral boronic acids to other compounds in situ was also demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Wei Wu, Shunli Wen, Xinyu Zhang, Qi Lin, Zhiqiang Weng
Summary: A highly efficient and regioselective synthesis of highly substituted 2-trifluoromethyl pyrrole derivatives is reported via a silver-catalyzed cyclization of vinyl azides with ethyl 4,4,4-trifluoro-3-oxobutanoate. Various types of alpha-(heteo)aryl, alkyl, alpha-aryl, and alpha,beta-disubstituted vinyl azides can participate in this transformation. The proposed reaction mechanism involves the addition of in situ generated 2H-azirine to the diketone species, followed by intramolecular addition, N-C-1 cleavage, and elimination.
Review
Chemistry, Multidisciplinary
Diksha Gambhir, Sanjay Singh, Ravi P. Singh
Summary: The rational combination of two catalysts has been widely used in the synthesis of biologically and pharmacologically relevant chiral compounds. This review article focuses on the achievements in asymmetric catalysis and synthesis using enamine and iminium-based dual organocatalytic systems. The combination of enamine/iminium catalysis with other organocatalytic systems has paved the way for the construction of complex chiral compounds.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Applied
Yongkai Pan, Qianwen Jiang, Subramani Rajkumar, Chaofan Zhu, Jinglei Xie, Shaoze Yu, Yunrong Chen, Yu-Peng He, Xiaoyu Yang
Summary: A series of cyclohexyl-fused SPINOL-derived phosphoric acids have been developed for the kinetic resolution of 2-N-acylamido tertiary allylic alcohols, providing access to chiral oxazolines with high enantioselectivities. Gram-scale reactions with 1 mol% catalyst loading and transformations of the chiral products demonstrate the value of these methods.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Hefei Yang, Shu-Ning Lu, Zhengkai Chen, Xiao-Feng Wu
Summary: This study developed a silver-mediated chemical reaction for the rapid assembly of 5-(trifluoromethyl)imidazoles, featuring readily accessible reagents, a broad substrate scope, and high efficiency. The protocol can be successfully applied to construct analogues of specific allosteric modulators of GABA(A) receptors, with the silver species being recyclable through simple operation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Andrea Guerrero-Corella, Miguel A. Valle-Amores, Alberto Fraile, Jose Aleman
Summary: An asymmetric organocatalytic aza-Michael addition reaction of ketimines to nitroolefins is described, utilizing 2-hydroxybenzophenone imine to improve the enantioselective addition of N-centered nucleophiles to nitroalkenes. The versatility of the process is demonstrated under both batch and flow conditions, resulting in the synthesis of a wide variety of nitroamine derivatives with excellent yields and enantioselectivities. Additionally, this methodology was successfully applied to the formal synthesis of VNI, a drug-like scaffold for the treatment of Chagas disease.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Hongli Chai, Xiang Zhen, Xueqing Wang, Liang Qi, Yuji Qin, Jijun Xue, Zhaoqing Xu, Hongrui Zhang, Weiwei Zhu
Summary: In this study, a hypervalent iodine catalyst was utilized for the nucleophilic fluorination of unsaturated amides, using BF3·Et2O as the fluorine source and activating reagent. Various 5-fluoro-2-oxazoline derivatives were synthesized with good to excellent yields (up to 95% isolated yield) within a short time of 10 minutes. The process was efficient, metal-free, and conducted under mild conditions. A proposed mechanism involving fluorination/1,2-aryl migration/cyclization cascade was based on previous studies and experimental results.
Article
Chemistry, Organic
Yuan-Zheng Wang, Le'an Hu, Shao-Tao Bai, Xumu Zhang
Summary: A user-friendly and simple catalytic method for the synthesis of high value primary &α;-(trifluoromethyl)aryl-methylamines via ruthenium-catalyzed asymmetric reductive amination of aryl-trifluoromethylketones using cheap NH4OAc as the nitrogen source and H-2 as the reductant is reported. This method tolerates various aromatic functions with electron-withdrawing or -donating substituents, as well as challenging heteroaromatic functions, leading to the formation of primary &α;-(trifluoromethyl)aryl-methylamines with excellent chemoselectivities, enantioselectivities, and useful yields (80-97% ee, 51-92% isolated yields).
Article
Chemistry, Multidisciplinary
Azusa Kondoh, Takayuki Hirozane, Masahiro Terada
Summary: In this study, a formal enantioselective umpolung addition method was developed under Bronsted base catalysis, which efficiently generated enantio-enriched phosphates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Huimyoung Byeon, Sunghyeon Ryu, Eun Jeong Yoo, Jung Woon Yang
Summary: Substrate-controlled cascade reactions between alpha,beta-unsaturated aldehydes or their analogues and 2,4-dinitrobenzyl chloride in the presence of a chiral secondary amine catalyst and base lead to a variety of alpha-benzylated enals and enantioenriched cyclopropane-fused chroman-2-one derivatives. The cyclopropane-tethered iminium ion plays a key role in these reactions to determine stereochemical outcomes, supported by a control experiment.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Tom D. D'Arcy, Mark R. J. Elsegood, Benjamin R. Buckley
Summary: The highly enantioselective organocatalytic tandem o-HPD-[4+2] reaction described offers a practical method for the synthesis of complex scaffolds. This approach utilizes a chiral oxaziridinium organocatalyst to afford dearomatized products in high enantioselectivity, demonstrating its potential for gram-scale applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Wei Liu, Tianren Qin, Wansen Xie, Xiaoyu Yang
Summary: Helicenes and helicene-like molecules with unique helical chirality have found wide applications in various research fields. However, the catalytic enantioselective synthesis of helicenes has been relatively underexplored. In the past two decades, significant progress has been made in this field, including methods enabled by both transition metal catalysis and organocatalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Adrien Quintard
Summary: In the past decade, multi-catalysis has become a popular alternative to traditional methods, offering rapid, efficient, and environmentally friendly ways to synthesize complex organic molecules. The use of iron-based catalysts has emerged as a cost-effective solution, with the added benefit of diverse reactivity features that expand the chemist's toolbox. These advantages position iron-based multi-catalysis as a leading technology for the future.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Shang-Hai Yu, Tian-Jun Gong, Yao Fu
Summary: A cooperative Cu/Pd-catalysed borylallenylation of 2-trifluoromethyl-1,3-enynes with propargylic carbonates under mild reaction conditions was developed, providing facile and efficient access to conjugated bisallenes with a broad range of functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Amparo Sanz-Marco, Daniel Esperilla, Marc Montesinos-Magraner, Carlos Vila, M. Carmen Munoz, Jose R. Pedro, Gonzalo Blay
Summary: A Cu(ii)/BOX complex catalyst was used for the enantioselective addition of difluorinated silyl enol ethers to acylpyridine N-oxides. The reaction produced difluorinated chiral tertiary alcohols, which are of great interest in medicinal chemistry. The reaction had good to excellent yields and high enantioselectivities. The stereochemical outcome of the reaction was explained by DFT calculations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Miguel Gavara-Edo, Francisco Javier Valverde-Munoz, Rosa Cordoba, M. Carmen Munoz, Javier Herrero-Martin, Jose Antonio Real, Eugenio Coronado
Summary: In this study, three new neutral Fe(II) SCO molecules belonging to the {Fe[H2B(pz)(2)](2)(L)} family were synthesized, and their crystallographic structure and magnetic properties were investigated. These compounds exhibited thermal- and light-induced SCO transitions with different degrees of cooperativity and effectiveness. Furthermore, two of the compounds were demonstrated to be sublimable, forming homogeneous thin films that retained the chemical integrity of the original molecules. SCO/2D horizontal hybrid devices based on CVD-graphene were successfully produced using these films, enabling the detection of the thermal SCO transition through the electric properties of CVD-graphene.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Alejandro Orellana-Silla, Ruben Turo-Cortes, Victor Rubio-Gimenez, Carlos Bartual-Murgui, Rob Ameloot, Carlos Marti-Gastaldo, M. Carmen Munoz, Jose Antonio Real
Summary: This study investigates the influence of chemical functionalization on the magnetic and adsorption properties of porous Fe-II coordination polymers. The results show that the chemical functionalization leads to significant changes in the magnetic transition temperature and curve shape, as well as higher adsorption capacities. The structural reasons behind these variations are determined through single crystal-to-single crystal transformations.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Laura Carceller-Ferrer, Gonzalo Blay, M. Carmen Munoz, Jose R. Pedro, Carlos Vila
Summary: A diastereo- and enantioselective synthesis of spirocyclopropylpyrazolones was achieved through a Michael/alkylation cascade reaction of 4-arylidenepyrazol-5-ones with diethyl 2-bromomalonate catalyzed by (DHQ)(2)AQN. The corresponding spirocyclic compounds were obtained selectively with yields of 30-83%, diastereoselectivities ranging from 60:40 to >95:5, and enantiomeric excess of 26-93% under mild reaction conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Jaume Rostoll-Berenguer, Gonzalo Blay, Jose R. Pedro, Carlos Vila
Summary: Financial support is acknowledged from grant PID2020-116944GB funded by MCIN/AEI/10.13039/501100011033, and by ERDF A way of making Europe and CIAICO/2021/147 funded by Conselleria d'Innovacio, Universitat, Ciencia i Societat Digital. J.R.-B. thanks the Ministerio de Ciencia, Innovacion y Universidades for a FPU predoctoral contract (FPU17/00688). C.V. thanks the RyC contract (RYC-2016-20187) funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGeneration EU/PRTR. Access to NMR, MS, and X-ray facilities from the Servei Central de Suport a la Investigacio Experimental (SCSIE)-UV is also acknowledged.
Article
Chemistry, Multidisciplinary
A. Carretero-Cerdan, S. Carrasco, A. Sanz-Marco, A. Jaworski, B. Martin-Matute
Summary: A microwave-assisted protocol for the synthesis of MIL-101(Cr) and MIL-101(Cr)-NH2 in only 1 hour with high crystallinity and yields (>70%, 0.5 g) using NaF as the modulator instead of hydrofluoric acid was described. Compared to traditional solvothermal protocols (12-72 h, <30%), the microwave-assisted synthesis enabled shorter reaction time and improved yields, with water replacing N,N-dimethylformamide. The physicochemical properties of MIL-101(Cr)-NH2 and MIL-101(Cr) obtained through this method showed better homogeneity, enhanced control over nanometric particle size, lower polydispersity, and higher Brunauer-Emett-Teller surface area.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jaume Rostoll-Berenguer, Victor Garcia-Garcia, Gonzalo Blay, Jose R. Pedro, Carlos Vila
Summary: This study describes an organophotoredox 1,6-radical addition of 3,4-dihidroquinoxalin-2-ones to para-quinone methides catalyzed by Fukuzumi's photocatalyst under the irradiation of a HP Single LED (455 nm). The corresponding 1,1-diaryl compounds bearing a dihydroquinoxalin-2-one moiety (20 examples) were obtained with good to excellent yields under mild reaction conditions. Several experiments were carried out to propose a reaction mechanism.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Borja Ortin-Rubio, Jaume Rostoll-Berenguer, Carlos Vila, Davide M. Proserpio, Vincent Guillerm, Judith Juanhuix, Inhar Imaz, Daniel Maspoch
Summary: In this study, a generalized net-clipping approach is proposed for predicting the topology of metal-organic frameworks (MOFs) constructed from less-symmetric ligands. The approach generates less-symmetric nets with less-connected linkers through the deconstruction of more-symmetric and more-connected linkers in edge-transitive nets. The researchers successfully applied this approach to different types of linkers, resulting in several new derived and clipped nets. The feasibility of using net-clipping to predict clipped nets is supported by literature examples and new experimental additions, demonstrating the significance of this method in the rational design of new reticular materials.
Article
Chemistry, Organic
Ricardo Toran, Eduardo Portillo, Amparo Sanz-Marco, Carlos Vila, Gonzalo Blay
Summary: We report the enantioselective arylation of isoxazolin-5-ones using a bifunctional squaramide derived from Cinchona alkaloid as a catalyst. The reaction proceeds with high yields and excellent enantioselectivities, resulting in isoxazolin-5-ones featuring an arylated quaternary stereocenter. This study represents the first application of o-QDIs as arylating reagents in asymmetric catalysis.
ORGANIC CHEMISTRY FRONTIERS
(2023)
