Review
Chemistry, Applied
Daniel Gavina, Marcos Escolano, Javier Torres, Gloria Alzuet-Pina, Maria Sanchez-Rosello, Carlos del Pozo
Summary: Substituted and annulated pyrroles containing chiral centers can be accessed through organocatalytic enantioselective Friedel-Crafts alkylation (FCA) reaction. These compounds are interesting due to their natural occurrence and diverse biological activities. In the past two decades, significant synthetic efforts have been made to develop asymmetric transformations involving pyrroles in the FCA reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Juan J. Rojas, Elena Torrisi, Maryne A. J. Dubois, Riashat Hossain, Andrew J. P. White, Giovanni Zappia, James J. Mousseau, Chulho Choi, James A. Bull
Summary: This paper reports a method for synthesizing 1,4-dioxanes and explores the catalytic mechanism of the reaction. The reaction exhibits high regio- and diastereoselectivity, and the resulting products serve as interesting motifs for drug discovery.
Article
Chemistry, Organic
Takanori Shibata, Mio Sasaki, Masafumi Kojima, Mamoru Ito
Summary: The chiral Ir(I)-catalyzed intermolecular reaction of N-carbamoylpyrrole and indole derivatives with alpha,beta-unsaturated carbonyl compounds proceeded with high enantioselectivity, yielding chirally functionalized pyrroles and indoles as formal C-H conjugate adducts. The reaction mechanism was further investigated through deuterium labeling experiments.
Article
Chemistry, Physical
Subhrajyoti Ghosh, Nagarathinam Nagarjun, Masud Alam, Amarajothi Dhakshinamoorthy, Shyam Biswas
Summary: The di-amide functionalized Zr(IV) metal-organic framework demonstrated high thermal and chemical stability, as well as noticeable catalytic performance in the Friedel-Crafts alkylation reaction. The catalyst also exhibited a broad substrate scope for the synthesis of various heterocyclic compounds, indicating effective promotion of reactions to achieve higher yields through appropriate design.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Organic
Jianguo Yang, Saimei Liu, Jing Gui, Daokai Xiong, Jinshan Li, Zhiming Wang, Jun Ren
Summary: A highly selective hydroxyalkylation of aniline derivatives with arylglyoxal hydrates has been achieved using HFIP as a catalyst. The reaction provides efficient synthesis of various N,N-dialkylanilines and their derivatives with alpha-hydroxy carbonyl units under mild conditions. The method has shown great synthetic potential by enabling the facile synthesis of several structurally interesting molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Weizhi Gu, Jindong Li, Kuiliang Li, Qi Sun, Tong Li, Zhenggen Zha, Zhiyong Wang
Summary: An asymmetric Mannich reaction of 2-fluoroindanone with ketimine was developed using a chiral copper complex catalyst, resulting in the formation of a chiral tetrahedral center containing fluorine. The reaction yielded a series of fi-fluoroamine derivatives in excellent yields (73-94%) with high diastereoselectivities (>99:1 dr) and enantioselectivities (89-99%). Density functional theory calculations supported the proposed transition state.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Haipeng Hu, Xin Wu, Yuqian Qiu, Cuilin Wang, Wei Wang, Guizhou Yue, Hanguang Wang, Juhua Feng, Guangtu Wang, Hailiang Ni, Ping Zou
Summary: In this study, the dehydrative mono-/dialkylation reactions of alcohols and beta-ketoacids were achieved under arylboronic acid catalysis, leading to the formation of beta-aryl ketones and beta-ketoesters in moderate to high yields. The reaction temperature was found to control the selectivity between decarboxylative alkylation and decarboxylation processes. A possible catalytic cycle was proposed based on experimental evidence.
Review
Chemistry, Multidisciplinary
Shenghan Teng, Jianrong Steve Zhou
Summary: This review summarizes the recent advances in transition metal-catalyzed asymmetric alkylation of heteroarenes using alkenes, covering literature from 2000 to late 2021. The reactions are classified into different categories based on the metal-mediated substrate activation, and the corresponding reaction mechanisms and catalyst design are discussed.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Fan Xiao, Peiqin Liao, Xiaoguang Lu, Jin Wang, Xiu-Qin Dong, Chun-Jiang Wang
Summary: In this study, an Ir-catalyzed asymmetric cascade reaction was successfully developed for the synthesis of chiral oxazinoindolone compounds with high efficiency. The method can be applied to pyrroles and other nitrogen-containing aromatic heterocycles. The reaction pathway was proposed based on preliminary mechanistic investigation. Importantly, the key intermediate for marine alkaloid (+)-agelastatin A can be readily accessed using this methodology.
Article
Chemistry, Organic
Amjad Ali, Raveena Jajoria, Harish K. Harit, Ravi P. Singh
Summary: In this study, the addition of alpha-ketoamide top-quinone methide initiated by dialkylphosphite in the presence of organic base DBU was explored. The coupling of dialkylphosphites to alpha-ketoamides followed[1,2]-phospha-Brook rearrangement, generating alpha-phosphonyloxy enolates that were subsequently seized by p-quinonemethides. This two-step one-pot 1,6-conjugate addition method provides effective access to a series of isatin-incorporated phosphate-bearing 1,6-adducts with high yield and selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yunlong Zhao, Rou Xiao, Weibin Fang, Junling Zhao
Summary: This study presents a protocol for the highly selective addition reaction of isatin-derived beta,gamma-unsaturated alpha-ketoesters with 4-aminoindoles at the C7 position. The reaction, catalyzed by a SPINOL-derived chiral phosphoric acid, yields bisindole derivatives with up to 97% enantiomeric excess. Further biological testing revealed that the products have high cytotoxicity against various cancer cell lines.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jake J. Blackner, Deirdre M. Rooney, Joshua W. Hollett, J. Adam McCubbin
Summary: A boronic acid catalyzed carbon-carbon and carbon-nitrogen bond-forming reaction using ferrocenium boronic acid hexafluoroantimonate salt as catalyst has been developed for the functionalization of various pi-activated alcohols. The reaction proceeds under mild conditions and yields up to 98%, with higher yields and selectivity observed when using organosilane nucleophiles. Computational studies provide a mechanistic pathway for the retention of E/Z stereochemistry when using alkenyl silanes as nucleophiles. This methodology is effective with a variety of organosilane nucleophile sub-types, including allylic, vinylic, and propargylic trimethylsilanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jia-Qi Wu, Xin-Yuan Wu, Jian-Mei Lu, Qian Shi, Li-Xiong Shao
Summary: In this study, a novel La(III)-based two-dimensional metal-organic framework was synthesized and used as an efficient Lewis acid catalyst for the Friedel-Crafts alkylation reaction. The catalyst exhibited a unique structure, good stability and catalytic activity in acidic and basic environments.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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
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, Inorganic & Nuclear
Maksym Seredyuk, Kateryna Znovjyak, Francisco Javier Valverde-Munoz, M. Carmen Munoz, Volodymyr M. Amirkhanov, Igor O. Fritsky, Jose Antonio Real
Summary: This paper reports a series of neutral trans-thiocyanate mononuclear spin crossover complexes based on tetradentate ligands L. These complexes exhibit thermal-induced spin crossover behavior and the formation of photo-generated metastable high-spin phases.
INORGANIC 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)
Article
Materials Science, Multidisciplinary
Alejandro Orellana-Silla, Manuel Meneses-Sanchez, Ruben Turo-Cortes, Victor Rubio-Gimenez, Giel Arnauts, M. Carmen Munoz, Rob Ameloot, Carlos Bartual-Murgui, Jose Antonio Real
Summary: Functionalization of spin crossover porous coordination polymers (PCPs) with hydrogen-bonding active groups is an efficient strategy for the study of multifunctional materials. The interaction of guests with the host framework can improve the cooperativity of the spin crossover (SCO) and further enhance its properties. Comprehensive magneto-structural studies are still needed to understand the role of guests in the enhancement of the SCO properties.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
