Article
Multidisciplinary Sciences
Zikun Wang, Zhansong Zhang, Wanjun Zhao, Paramasivam Sivaguru, Giuseppe Zanoni, Yingying Wang, Edward A. Anderson, Xihe Bi
Summary: The authors synthesized previously thought to be unstable sulfonyl sulfones and demonstrated their broad use as sulfinyl radical precursors in disulfurizations of alkenes and alkynes. Experimental and theoretical investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl radical addition.
NATURE COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Zixu Zhang, Xinru Wang, Paramasivam Sivaguru, Zikun Wang
Summary: Sulfinyl radicals, sulfur-centered pi-radicals, have made significant progress in synthetic chemistry in recent years. This review summarizes the potential applications, challenges, and future development trends of sulfinyl radicals in modern organic chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Biochemistry & Molecular Biology
Ana Sofia Almeida, Barbara Silva, Paula Guedes de Pinho, Fernando Remiao, Carla Fernandes
Summary: New psychoactive substances, such as synthetic cathinones, pose a public health threat as they are easily accessible online and often sold as legal alternatives to illicit drugs. Synthetic cathinones are widely abused due to their stimulating and hallucinogenic effects. However, their chemical and toxicological properties remain unknown, as new derivatives continue to emerge on the drug market. This review focuses on the recent developments in synthetic cathinones, including over 50 derivatives since 2014, and highlights the importance of enantioselectivity studies and enantioseparation analysis in understanding their biological and toxicological activities.
Article
Chemistry, Physical
Da Xu, Yu Chang, Yidong Liu, Wenling Qin, Hailong Yan
Summary: This study achieved the enantioselective construction of stable VQM intermediates through organocatalyzed bromination, and revealed the mechanistic details of the two sequential events in VQM-involved reactions. The high potential of VQM as axially chiral synthetic reagents in organic chemistry was demonstrated.
Article
Chemistry, Organic
Hao Deng, Yujie Dong, Yu Shangguan, Fazhou Yang, Sheng Han, Jiaqi Wu, Bo Liang, Hongchao Guo, Cheng Zhang
Summary: A diastereoselective copper and NHC-ligand-catalyzed three-component difunctionalization of allenes with bis(pinacolato)diboron and 2H-azirines to afford borylated allylaziridines has been reported, showing complete diastereoselectivity and good yields. The high ring-strain force of 2H-azirines is believed to facilitate the reaction, and further chemical transformations of borylated allylaziridines have been explored.
Article
Chemistry, Multidisciplinary
Guolin Wu, Yuan Yao, Gen Li, Xue Zhang, Hui Qian, Shengming Ma
Summary: This study developed a catalytic recipe of copper halides to address the issues of side reactions and selectivity in the 1,5-H transfer of alka-1,4-diyn-3-yl amines, providing various allenynes with excellent enantioselectivities. The method was successfully applied to the first highly enantioselective total synthesis of the natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5-H transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zhen Luo, Zheng-Qiang Liu, Ting-Ting Yang, Xin Zhuang, Chuan-Ming Hong, Fei-Fei Zou, Zhi-Yong Xue, Qing-Hua Li, Tang-Lin Liu
Summary: A highly selective and catalyst-free sulfonation of allylic alcohols with sulfinyl amides has been achieved, providing a convenient way to synthesize various allylic sulfones under mild conditions. This novel reaction exhibits broad substrate scope and excellent functional group tolerance, and can also be scaled-up. In addition, sulfinyl amides have been found to act as powerful sulfur nucleophiles in this reaction. Moreover, the solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) plays a crucial role in allylic sulfonation.
Article
Chemistry, Applied
Pablo Esteban, Fernando Herrera, Daniel San Martin, Amparo Luna, Pedro Almendros
Summary: Typical transition metal-catalyzed oxycyclization reactions can lead to the formation of different products via distinct mechanisms, such as the 5-endo cyclization to form dihydrofurans or the 3-exo-cyclization/sulfonylation cascade to generate trisubstituted epoxides. The current stoichiometry control of regioselectivity may offer unique opportunities for chemical transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Fernando Herrera, Pablo Esteban, Amparo Luna, Pedro Almendros
Summary: The synergy between metal catalysis and radical chemistry has enabled researchers to overcome previous limitations in reactions between allenols and sulfonylating reagents, leading to successful copper-catalyzed cascade cycloetherification/sulfonylation for the controlled preparation of specific products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Chaoyan Ma, Can Li, Jiahui Bai, Junzhe Xiao, Yizhan Zhai, Yinlong Guo, Shengming Ma
Summary: In this study, a rhodium-catalyzed C-H functionalization-based intermolecular allylation of indoles with trisubstituted allenes has been developed. The synthetic process demonstrates excellent regioselectivity, Z-selectivity, high efficiency of chirality transfer, and a wide tolerance of reactive functional groups under mild conditions. Late-stage modification on complex bioactive or drug molecules has been achieved, along with various synthetic transformations. A reaction mechanism has been proposed based on mechanistic experiments and SAESI-MS studies.
Article
Chemistry, Multidisciplinary
Sandra Miguez-Lago, Bettina D. Gliemann, Milan Kivala, Maria Magdalena Cid
Summary: In this paper, scientists reported the synthesis and characterization of a chiral shape-persistent molecular cage based on the combination of enantiopure diethynylallenes and electron-rich bridged triarylamines. The experimental results revealed that this molecular cage has good chiral recognition ability in solution.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Correction
Chemistry, Organic
Mengning Wang, Qiuzhu Wang, Mengtao Ma, Binlin Zhao
Summary: The article discusses a copper-catalyzed method for synthesizing trifluoromethyl allenes through fluoro-carboalkynylation of alkenes. The method shows great potential for applications.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Yunhe Lv, Jinhui Xie, Weiya Pu, Xue Wang, Huanhuan Zhang, Xuerui Li, Yan Liu, Fei Chen, Yunfeng Xu
Summary: We developed a strategy for the copper-catalyzed three-component reaction to synthesize tetrasubstituted allenes with phosphinoyl and cyano groups. The reaction exhibited high functional group compatibility and good yields under mild conditions. A preliminary reaction mechanism involving the formation of phosphinoyl radicals and their regioselective addition to 1,3-enynes was proposed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Maria Lago-Silva, Maria Magdalena Cid, Emilio Quinoa, Felix Freire
Summary: This article presents a new mechanism for helix inversion in polymers, which is achieved by activating/deactivating supramolecular interactions. The screw sense of the polymer is fixed by the spatial orientation of the substituents, but can be reversed through supramolecular interactions and external stimuli.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Nanoscience & Nanotechnology
Jian-Qi Zhang, Jing-Xin Liu, Hui-Lai Zhang, Zhi-Rui Gong, Shuo Zhang, Lei-Lei Yan, Shi-Lei Su, Hui Jing, Mang Feng
Summary: This study proposes a method to achieve synthetic PT symmetry in optomechanics without using any active medium. By harnessing the Stokes process, exceptional points (EPs) can emerge, leading to nonreciprocal optical amplification and chiral mode switching. This provides a simplified route to realize PT-symmetric optomechanics and enables the creation and utilization of EP devices for various applications.
Article
Chemistry, Multidisciplinary
Ricardo Rodriguez, Marina Sicignano, Jose Aleman
Summary: In this study, a convenient strategy using gem-difluorinated sulfinates as upgrading-masks is reported, which allows the decomposition of precursors into corresponding alkyl radicals. The stereocontrolled light-driven insertion of gem-difluoro derivatives into unsaturated aldehydes is achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Miguel A. Valle-Amores, Ana M. Martinez-Gualda, Leyre Marzo, Alberto Fraile, Jose Aleman
Summary: A visible-light mediated strategy for the synthesis of cyclic beta-amino carbonyl derivatives with three contiguous stereogenic centers is introduced. The reactivity of the transformation relies on the substrate-catalyst complex to assist both enantioselectivity control and photoredox reactions. This transformation enables an enantioselective [3 + 2] photocycloaddition between coordinated alpha,beta-unsaturated acyl imidazoles and cyclopropylamine derivatives.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Miguel A. Valle-Amores, Matias Blanco, Stefano Agnoli, Alberto Fraile, Jose Aleman
Summary: This article presents a carbocatalytic synthesis method using mild-oxidized multiwalled carbon nanotubes catalyst as a carrier to achieve a smooth condensation reaction between aldehydes and hydrazine, resulting in the formation of azines. The method shows excellent yields and selectivity for aromatic substrates, with potential applications in nonlinear optics, organic materials, and biological active compounds crafting.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Andrzej Nowok, Wioleta Cieslik, Mateusz Dulski, Karolina Jurkiewicz, Joanna Grelska, Jose Aleman, Robert Musiol, Anna Z. Szeremeta, Sebastian Pawlus
Summary: This article uses a combination of quantum computations and various studies to analyze the nature of atypical bifurcated hydrogen bonds (BHBs). The experiments prove that self-organization through BHBs is prevalent in H-bonding systems, even with high screening of proton-donor and proton-acceptor groups. It is also shown that even highly sterically hindered Schiff bases can form lasting centrosymmetric dimers through BHBs. The driving force for their ordering tendency is the disorder in the molecular scaffold.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Green & Sustainable Science & Technology
Alberto Lopez-Magano, Ruben Mas-Balleste, Jose Aleman
Summary: The study demonstrated the stable coordination of palladium centers by the phenanthroline unit in Phen-COF, leading to enhanced catalytic activities and recyclability. The concept of isolating and immobilizing catalytic sites in Pd@Phen-COF significantly improved catalytic outputs compared to analogous molecular catalysts, particularly in C-C cross-coupling reactions.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Nanoscience & Nanotechnology
Alicia Jimenez-Almarza, Alberto Lopez-Magano, Ruben Mas-Balleste, Jose Aleman
Summary: Three materials with different pore structures were studied for the visible light-mediated oxidative coupling of amines. The triazine-based material showed the best compromise between activity and stability, allowing for multiple catalytic cycles with high yields.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Applied
Noelia Salaverri, Benedetta Carli, Patricia B. Gratal, Leyre Marzo, Jose Aleman
Summary: The application of proton coupled electron transfer (PCET) processes in organic synthesis has allowed for the introduction of new radical intermediates, such as alkyl radicals, into synthesis. In this study, remote alkyl radicals were added to electron deficient double bonds under mild conditions using photoorganocatalysis. The method is not only applicable to diactivated double bonds, but can also be used for monoactivated ones by using more stable alkyl radicals. Furthermore, alkyl chains of various lengths can be introduced. The resulting products can easily be converted into more complex structures through a one-pot process, with activating functional groups transformed into methyl esters. Mechanistic investigations support the proposed PCET process.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Biochemistry & Molecular Biology
Andrzej Nowok, Wioleta Cieslik, Joanna Grelska, Karolina Jurkiewicz, Natalina Makieieva, Teobald Kupka, Jose Aleman, Robert Musiol, Sebastian Pawlus
Summary: The surprising stability of supercooled liquid phase in Schiff base compounds, even under high-pressure conditions, and the atypical self-organization into lasting centrosymmetric dimers through bifurcated hydrogen bonds have been revealed. General rules governing ambient- and high-pressure molecular dynamics and near-glass transition phenomena have been derived for the family of glycine imino esters. Particularly, a mathematical formula to predict and tune the glass transition temperature and its pressure coefficient has been derived.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Pharmacology & Pharmacy
Tugce Boztepe, Sebastian Scioli-Montoto, Rocio C. Gambaro, Maria Esperanza Ruiz, Silvia Cabrera, Jose Aleman, German A. Islan, Guillermo R. Castro, Ignacio E. Leon
Summary: Colorectal cancer, the second leading cause of cancer death, is referred to as colon or rectal cancer depending on the site of formation. The platinum-based compound 8-QO-Pt has shown promising anticancer activity. In this study, three different systems of 8-QO-Pt-encapsulated nanostructured lipid carriers (NLCs) with riboflavin (RFV) were investigated. The results demonstrated the higher cytotoxicity of the 8-QO-Pt-loaded NLC/RFV formulations compared to free 8-QO-Pt, indicating the potential of RFV-targeted NLC systems for colon cancer treatment.
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Roberto del Rio-Rodriguez, Jose A. Fernandez-Salas, Jose Aleman
Summary: This work presents an electrochemical method for synthesizing allyl sulfones by sulfonating allyl trifluoroborates. The process involves a radical addition to the alkene and subsequent elimination of the trifluoroborate moiety, leading to the formation of substituted allyl sulfones. The reaction is highly efficient and versatile, compatible with various aromatic, heteroaromatic, and aliphatic systems. It offers a cost-effective and environmentally friendly approach for synthesizing recognizable organic motifs in both synthetic and medicinal chemistry.
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Roberto del Rio-Rodriguez, Jose A. Fernandez-Salas, Jose Aleman
Summary: This work describes the electrochemical synthesis of allyl sulfones via sulfonation of allyl trifluoroborates. The process is efficient and versatile, and does not require a mediator or additional supportive electrolyte, making it a cost-effective, safe, and environmentally friendly method for synthesizing this recognizable organic motif. The high selectivity of the sulfonation reaction is attributed to the stability of the electrochemically-generated intermediate carbocation.
Article
Chemistry, Organic
Miguel A. Valle-Amores, Claudia Feberero, Ana Martin-Somer, Sergio Diaz-Tendero, Andrew D. Smith, Alberto Fraile, Jose Aleman
Summary: In this study, a highly enantioselective organocatalyzed [3 + 2] cycloaddition reaction between furanone derivatives and azomethine ylides was presented. The success of this reaction is attributed to intramolecular hydrogen bond activation and the formation of highly multifunctional bicyclic adducts with five stereogenic centers. The reaction also achieved a highly efficient kinetic resolution of butenolides, leading to the formation of furan-2(5H)-ones and furo[3,4-c]pyrrolidinones with high enantioselectivities. Quantum chemistry calculations revealed the crucial role of hydrogen bonding in promoting facial discrimination and achieving a highly selective kinetic resolution.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jose Luis Nova-Fernandez, Montana J. Garcia, Leonardo Mollari, Gustavo Pascual-Coca, Silvia Cabrera, Jose Aleman
Summary: A sustainable strategy for alkylation of heterocycles is proposed, which involves the in situ generation and further in-line use of alkyl zinc sulfinates through a continuous-flow system. The protocol demonstrates environmentally friendly characteristics by employing a green solvent mixture, a metal-free oxidant, and low waste generation.
CHEMICAL COMMUNICATIONS
(2022)
