Article
Chemistry, Organic
Soumen Biswas, Luca De Angelis, Gildardo Rivera, Hadi Arman, Michael P. Doyle
Summary: 1,2,3-Triazine 1-oxides are highly effective substrates for inverse electron demand Diels-Alder reactions. These stable heterocyclic compounds, formed from vinyldiazoacetates via reaction with tert-butyl nitrite, undergo clean nucleophilic addition reactions with amidines to form pyrimidines, with beta-ketocarbonyl compounds and related nitrile derivatives to form polysubstituted pyridines, and with 3/5-aminopyrazoles to form pyrazolo[1,5-a]pyrimidines, in high yields. These reactions, catalyzed by bases, are rapid at room temperature and allow for a range of structural modifications.
Article
Chemistry, Organic
Jia-Hao Zeng, Ding-Chang Li, Sheng Zhang, Zhuang-Ping Zhan
Summary: This study presents a chemodivergent protocol for the synthesis of branched and linear allylic sulfones bearing a conjugated (Z,E)-1,3-diene scaffold by Pd-catalyzed coupling of allenes with sulfinic acids. The method features mild conditions, an unprecedented substrate scope, and functional group compatibility.
Article
Chemistry, Physical
Matyas Papai, Tamas Rozgonyi, Gyoergy Vanko
Summary: The application of N-heterocyclic carbene (NHC) ligands in light-harvesting complexes has made significant progress, but there are still controversies regarding the excited-state dynamics of Fe-NHC photosensitizers. Using simulations, this study clarifies the deactivation mechanism of [Fe(bmip)2](2+) and finds that the photosensitizing efficiency is weakened by the ultrafast quenching of the triplet metal-to-ligand charge transfer by metal-centered states. Experimental data also suggest the presence of early sub-picosecond metal-centered states.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Organic
Hyun Ji Jeon, Su Min Park, Yu Lim Lee, Sang-gi Lee
Summary: The palladium-catalyzed divergent asymmetric synthesis of chiral spiro-furanindoline derivatives is described. The zwitterionic alkoxy pi-allyl Pd(II) intermediate, generated catalytically from vinyl ethylene carbonate (VEC), could undergo ligand-controlled enantio-and diastereoselective dipolar [3 + 2] spiroannulation with indole-based azadienes to afford the optically active spiro-furanindolines embedding an all-carbon quaternary stereocenter in high yields (up to 99%) with good to excellent stereoselectivities (up to 99% ee and up to >94:6 dr).
Article
Chemistry, Organic
Guangxing Pan, Shaoheng Qin, Dawen Xu, Fritz E. Kuehn, Hao Guo
Summary: The photoinduced pericyclic cascade reaction described in this study provides a novel approach to oxabicyclo[4.2.0]octenes, involving [2 + 2]-photocycloaddition, base-promoted elimination, retro-4p-electrocyclization, [1,5]-H shift, and 4p-electrocyclization processes. This reaction exhibits broad substrate scope, good functional group tolerance, and excellent diastereoselectivity.
Article
Chemistry, Organic
Atif Sharif, Huai-Ri Sun, Wen-Lei Xu, Bo-Bo Gou, Lan Yang, Yu Li, Jie Chen, Ling Zhou
Summary: An efficient dehydrogenative inverse electron demand Diels-Alder reaction has been reported for the first time, providing a broad substrate scope and excellent yields in the synthesis of biologically valuable pyranones.
Article
Multidisciplinary Sciences
Rachel C. Epplin, Shashwati Paul, Loic Herter, Christophe Salome, Erin N. Hancock, Jay F. Larrow, Erich W. Baum, David R. Dunstan, Carol Ginsburg-Moraff, Thomas C. Fessard, M. Kevin Brown
Summary: The authors report the synthesis and development of ladderanes as replacements for meta-substituted aromatic rings and cyclohexanes. These compounds offer similar metabolic and physicochemical properties, establishing them as interesting motifs for drug discovery.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Soumitra Agasti, Frederic Beltran, Emma Pye, Nikolas Kaltsoyannis, Giacomo E. M. Crisenza, David J. J. Procter
Summary: A general synthetic route to substituted bicyclo[2.1.1]hexanes (BCHs) has been developed through intermolecular coupling between olefins and bicyclo[1.1.0]butyl (BCB) ketones. The SmI2-catalysed process can be applied to a wide range of electron-deficient alkenes and substituted BCB ketones, with low loadings of SmI2. The resulting BCH ketones have been shown to be versatile synthetic intermediates and can be used for selective downstream manipulation and the expedient synthesis of a saturated hydrocarbon analogue of the broad-spectrum antimicrobial, phthalylsulfathiazole.
Review
Chemistry, Multidisciplinary
Alberto Feliciano, Juan L. Vazquez, Luis J. Benitez-Puebla, Ivan Velazco-Cabral, David Cruz Cruz, Francisco Delgado, Miguel A. Vazquez
Summary: The structure of FCCs is electron-deficient and can undergo high-order cycloadditions to generate a variety of compounds, which have been widely used in organic synthesis to produce diverse scaffolds. Research shows that selectivity can be increased by exploring different reaction conditions and co-catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Evelina Liarou, Hannes A. Houck, Filip E. Du Prez
Summary: This article introduces a method of reversibly altering the topology of macromolecules using visible light and darkness as the only stimuli, achieving control over the shape of the polymer through cycloaddition and cycloreversion reactions, with great potential for various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yueshan Hou, Mingyue Cui, Keke Zhang, Lihui Chen, Rongqiang Tian
Summary: This study demonstrates that phosphole sulfides can act as 2 pi-electron components in cycloaddition reactions, achieving the [3 + 2] cycloaddition reaction between phosphole sulfides and nitrones.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yueshan Hou, Mingyue Cui, Keke Zhang, Lihui Chen, Rongqiang Tian
Summary: In this study, the [3 + 2] cycloaddition reaction between phosphole sulfides and nitrones was reported to afford phospholene fused isoxazolidine skeleton with high yields and excellent regioselectivity. The oxygen atom exclusively attaches to the beta carbon atom of the phosphole, and the C=C bond in the product does not react with the nitrone. This work demonstrates that slightly antiaromatic phosphole sulfides can act as 2 pi-electron components in cycloaddition reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Cooper S. Jamieson, Arkajyoti Sengupta, K. N. Houk
Summary: Through quantum mechanical studies and molecular dynamics simulations, it was found that the cycloadditions of cyclopentadiene and cycloheptatriene with tropone involve ambimodal transition states, leading to a complex network of products. This general concept was supported by calculations of simple parent systems and a thorough meta-analysis of literature examples.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Trevor A. Hamlin, F. Matthias Bickelhaupt, Israel Fernandez
Summary: Organic chemistry has had a significant impact on humanity, with common organic compounds such as pharmaceuticals, plastics, and fuels being synthesized through organic reactions. Despite the frequent use of Lewis acids and organocatalysts in catalyzing organic reactions, the concept of LUMO-lowering catalysis is found to be incomplete and not always effective.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Hong Ji, Juan Zou, Chengli Mou, Yonggui Liu, Shi-Chao Ren, Yonggui Robin Chi
Summary: In this study, a N-heterocyclic carbene (NHC) catalyzed enantio- and diastereoselective [12+2] cycloaddition was developed to rapidly construct complex molecules with a tricyclic core and morpholine moiety. The success of the reaction relied on the NHC-catalyzed remote sp(3) (C-H) bond activation of a 5H-benzo[a]pyrrolizine-3-carbaldehyde under oxidative conditions. Preliminary studies demonstrated that the products showed superior in vitro bioactivities against two plant pathogens compared to commercial Bismerthiazol (BT) and Thiodiazole Copper (TC).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Lei Ge, Hao Yuan, Yuxiang Min, Li Li, Shiqian Chen, Lai Xu, William A. Goddard
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Physical
Jing-Yi Zhu, Shiqian Chen, Qi Xue, Fu-Min Li, Hong-Chang Yao, Lai Xu, Yu Chen
APPLIED CATALYSIS B-ENVIRONMENTAL
(2020)
Article
Chemistry, Physical
Shiqian Chen, Hao Yuan, Sergey I. Morozov, Lei Ge, Li Li, Lai Xu, William A. Goddard
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Physical
Lei Ge, Weiwei Xu, Chongyang Chen, Chao Tang, Lai Xu, Zhongfang Chen
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Physical
Hao Yuan, Yuxiang Min, Lai Xu
Summary: In this study, a series of integrated CsPbBr3-CsPbCl3 heterostructures were designed to explore their catalytic capability for photocatalytic water splitting. The researchers found a connection between dopant atoms and catalytic performance, and proposed a new descriptor. The CsPbBr3:Ni-CsPbCl3:Co system showed promising potential for overall water splitting and better photocatalytic performance.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Yuxiang Min, Hao Yuan, Wugang Wang, Lai Xu
Summary: In this study, a combination of MXene and a two-dimensional organic framework was designed for Na-O-2 batteries, with Ti2CO2/Cu-BHT showing excellent performance including low OER and ORR overpotentials and moderate Eads(Na+). A new mechanism called the Na encapsulation mechanism was proposed on the surface of the two-dimensional organic framework. Through LASSO regression, a new descriptor consisting of inherent properties was found to help in screening better heterostructures for Na-O-2 batteries.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Yindong Gu, Yuxiang Min, Li Li, Yuebin Lian, Hao Sun, Dan Wang, Mark H. Rummeli, Jun Guo, Jun Zhong, Lai Xu, Yang Peng, Zhao Deng
Summary: This study presents the phenomenon of crystal splintering induced by interstitial atomic doping for enhancing the activities of both oxygen evolution and oxygen reduction reactions in beta-MnO2. The Ru-doped beta-MnO2 exhibits an ultralow OER and ORR voltage gap, surpassing many state-of-the-art bifunctional oxygen catalysts reported to date. The improved OER activity is attributed to the highly under-coordinated Ru-O sites exposed on the surface upon crystal splintering, while the enhanced ORR property originates from the strained M-O configuration with enriched Mn3+ content and oxygen vacancies.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Physical
Fan Liao, Siyu Chen, Yuwei Shen, Yanqing Li, Huixian Shi, Lai Xu, Wenxiang Zhu, Kui Yin, Mingwang Shao
Summary: The surface fluorinated nickel-graphene nano-composites synthesized via reduction of Si-H bonds in hydrothermal condition exhibit higher activity and kinetics for methanol oxidation reaction (MOR). The introduction of fluorine leads to the formation of nickelic, decreasing the reaction energy barrier for MOR. The strong electronegativity of fluorine atoms facilitates the attraction of OH- groups and repulsion of protons, contributing to the enhanced performance of F-Ni-G nanocomposites as MOR catalysts.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Electrochemistry
Xu Yuan, Yuxiang Min, Jingda Wu, Lai Xu, Wenbo Yue
Summary: This study focuses on the fabrication of PtZn intermetallic nanoparticles on a nitrogen-doped porous carbon support, which enhances the catalyst dispersibility and electrocatalytic performance. Adjusting the Pt/Zn mole ratio enables fine tuning of the catalyst's surface electronic structure, ultimately improving the efficiency of methanol oxidation reaction.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Wugang Wang, Soonho Kwon, Lai Xu, William A. Goddard
Summary: Heterostructure exhibits superior catalytic performance and the advantages of van der Waals interaction. This study constructs a vacancy-van der Waals heterostructure and predicts the Tafel slope of the catalytic reaction using grand canonical reaction kinetics.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Multidisciplinary
Siyu Chen, Yongqi Gao, Wugang Wang, Oleg V. Prezhdo, Lai Xu
Summary: In the study, it was found that introducing N vacancies and embedding three metal atom clusters in a two-dimensional metal nitride, W2N3, can enhance the electrocatalytic nitrogen reduction reaction (NRR). Among all the proposed catalysts, the VNiCu cluster showed the best catalytic activity. The Fe3 and Fe2Co clusters also exhibited excellent catalytic performance. Three groups of descriptors were identified to predict the materials' properties and were found to have linear relationships with the NRR limiting potential.
Article
Chemistry, Multidisciplinary
Dewei Zhang, Oleg V. Prezhdo, Lai Xu
Summary: Researchers have designed a two-dimensional carbon nitride material with excellent conductivity and stability, which supports the electrocatalytic CO2 reduction reaction. After screening multiple metal clusters, Cu4-C5N2H2 showed superior selectivity and low limiting potential for generating ethylene, while Cu2Zn2-C5N2H2 exhibited selectivity and efficiency for synthesizing ethanol. In addition, a novel descriptor related to the flexibility of 2D materials was discovered to evaluate the potential-determining step for generating ethylene. This study expands the possibilities for few-atom CO reduction and introduces a new substrate flexibility-related descriptor to predict catalytic performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Xin Cao, Chongyang Chen, Yuxiang Min, Hao Yuan, Shiqian Chen, Lai Xu
Summary: This study reported on homo/hetero bimetal embedded in two-dimensional materials for CO2 reduction catalysis. By choosing beta(12)-borophene to accommodate two transition metal atoms, MnCo and VV systems were found to have promising activity for CO2 reduction.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Li Li, Lai Xu
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Physical
Zhengzhe Xie, Wugang Wang, Ding Ding, Yu Zou, Yi Cui, Lai Xu, Jiang Jiang
JOURNAL OF MATERIALS CHEMISTRY A
(2020)