Article
Chemistry, Multidisciplinary
Aabid A. Wani, Kriti Mehta, Rajeswara Reddy, Prasad V. Bharatam
Summary: This article reports the 1,1-diaminoazine-catalysed Michael addition reaction of malonates with nitro-olefins. The bifunctional nature of the catalyst facilitates the C-C bond formation.
NEW JOURNAL OF CHEMISTRY
(2023)
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, Physical
Zhan-Cai Ma, Lin -Wen Wei, Song Liu, Yuan Huang
Summary: The synthesis of spirocyclic frameworks with multiple stereogenic centers through a single transformation is a high-priority challenge in synthetic chemistry. This study reports an unprecedented efficient stereodivergent [4+2] annulation reaction using palladium catalysts to synthesize spiropyrazolones with three contiguous stereogenic centers. Excellent diastereodivergency (up to >20:1) and enantioselectivity (up to >99% ee) have been achieved using different commercially available chiral ligands. This is the first example of employing vinyl benzoxazinanones as the palladium p-allyl precursor for stereodivergent reactions. Density functional theory (DFT) calculations provide insights into the mechanism of this stereodivergent annulation process.
Article
Chemistry, Organic
Luo-Yu Wang, Jiapei Miao, Yu Zhao, Bin-Miao Yang
Summary: We report a highly selective abbreviation for the efficient synthesis of 1,1'-biheteroaryls. Under the cooperative catalysis of chiral phosphoric acid and InBr3, reactions between 2,3-diketoesters and 1,3-dione-derived enamines resulted in the highly enantioselective construction of 1,1'-pyrrole-indoles with up to 92% yield and 94% enantiomeric excess. Derivatizations of these compounds to diverse functionalized N-N linked axially chiral biheteroaryls have also been demonstrated.
Article
Chemistry, Organic
Luo-Yu Wang, Jiapei Miao, Yu Zhao, Bin-Miao Yang
Summary: We developed a highly selective method for synthesizing 1,1'-biheteroaryls bearing a chiral N-N axis. By using chiral phosphoric acid and InBr3 as cooperative catalysts, 2,3-diketoesters reacted with 1,3-dione-derived enamines to construct 1,1'-pyrrole-indoles with high enantioselectivity, up to 92% yield, and up to 94% enantiomeric excess (ee), or bisindoles with up to 92% ee. Derivatizations of these compounds resulted in diverse functionalized N-N linked axially chiral biheteroaryls.
Article
Chemistry, Organic
Young Eum Hyun, Hong-Rae Kim, Lak Shin Jeong
Summary: Asymmetric synthesis was used to synthesize conformationally locked south (S) and north (N) analogues of sugars, with different synthetic strategies employed to obtain the two conformations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Aliyaah J. M. Rahman, Lucie Finck, Wolfgang Obermayer, Martin Oestreich
Summary: The transition-metal-free protocol allows for the arylation of N-phenyl and N-benzoyl-substituted, benzaldehyde-derived imine derivatives with functionalized aryl pronucleophiles. Aryl nucleophiles are released from silicon protected aryl-substituted diazenes through desilylation with potassium trimethylsilanolate, simultaneously losing dinitrogen.
Article
Chemistry, Organic
Jing Li, Zhonglin Wei, Jungang Cao, Dapeng Liang, Yingjie Lin, Haifeng Duan
Summary: A highly enantioselective aza-Friedel-Crafts reaction of 1H-indoles with isatin-derived N-Cbz-ketimines catalyzed by quinine-derived phase-transfer catalysts was developed. Chiral 3-aminobisindole compounds containing a tetrasubstituted stereocenter were constructed in high yields (82-91%) and moderate to excellent enantioselectivities (46-94% ee).
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Prantika Bhattacharjee, Utpal Bora
Summary: This review highlights the importance of remote regioselectivity in the metal-free organocatalytic functionalization of indoles in the carbocyclic ring positions up to the middle of 2020. Exciting developments have been achieved to access remote regioselectivities at the C4, C5, C6, and C7 positions of the indole core, overcoming the challenges posed by the dominant reactivity of the pyrrole core.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Zhen-yu Lu, Wei-qiao Lan, Fang-yi Liu, Jun-yi Wang, Xiao-mei Zhang, Li-hua Liao
Summary: An efficient catalytic asymmetric [3 + 2] cyclization of 3-substituted indoles with p-benzoquinones has been achieved using binol-chiral phosphoric acid. A variety of C3 substituted benzofuroindolines compounds were synthesized in moderate to high yields (up to 91% yield) and excellent enantioselectivities (up to 94% ee).
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Dong Xu, Yang Chen, Changmeng Liu, Jiaxi Xu, Zhanhui Yang
Summary: This study demonstrates a highly chemoselective and efficient transfer hydrogenation reduction of structurally diverse nitroalkenes with very low catalyst loading, achieving high turnover numbers and turnover frequencies without the need for an inert atmosphere. Reactivity is dependent on substitution pattern, with pH value being a key factor. Products can be purified through simple extraction, and the reduction process can be scaled up to 10 grams.
Article
Chemistry, Multidisciplinary
Pedro De Jesus Cruz, Jeffrey S. Johnson
Summary: Tetrasubstituted stereogenic carbon centers bearing a nitrogen substituent are important in medicinal chemistry and natural products. This article presents a method for the stereoselective synthesis of these compounds through stereoconvergent Henry reactions. The study demonstrates the use of crystallization-based stereocontrol to leverage the reversibility of the reactions and efficiently assemble complex acyclic stereoarrays.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Zeqing Duan, Min Liu, Bing Zheng, Yi Tang, Juan Du, Lei Wang, Songcheng Yu, Yongjun Wu, Hongchao Guo
Summary: The tandem annulation of allenylic alcohols with 1,1-dicyanoalkenes catalyzed by phosphine has been developed, leading to the synthesis of various bicyclic tetrahydrocyclopentafuran derivatives with yields ranging from 40% to 89% and moderate to excellent diastereoselectivities. The formation of the fused ring is achieved through a sequential (3 + 2) annulation/nucleophilic addition reaction. The unusual nucleophilic addition of an alkoxide ion to a cyano group results in the formation of a tetrahydrofuran ring with an imino substituent.
Review
Chemistry, Multidisciplinary
Hong-Hao Zhang, Feng Shi
Summary: Catalytic atroposelective synthesis of axially chiral indole derivatives is of considerable importance and has become an emerging focus of research. By designing indole-derived platform molecules and developing strategies for organocatalytic transformations, we have successfully synthesized structurally diversified indole derivatives with axial chirality. These platform molecules possess versatile and unique reactivity, allowing for the synthesis of various axially chiral indole derivatives.
ACCOUNTS OF CHEMICAL RESEARCH
(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)