Article
Chemistry, Multidisciplinary
Jackson S. Henneveld, Farshad Shiri, Alireza Ariafard, Nigel T. Lucas, Alex C. Bissember, Bill C. Hawkins
Summary: The investigation and formalization of the distinctive dipole-transmissive dipolar cycloaddition (DTDC) methodology is reported. A DTDC procedure was developed by taking advantage of the structural complementarity of azide and diazoalkane 1,3-dipoles. This method allows for the rapid construction of functionalized polycyclic N-heterocycles through intramolecular azide-alkene 1,3-dipolar cycloadditions followed by N-derivatization and subsequent 1,3-dipolar cycloadditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Cesar Barrales-Martinez, Pablo Jaque
Summary: This study investigates the role of synchronicity in the formation of new single bonds in a large set of 1,3-dipolar cycloadditions and its relation to the classical Bell-Evans-Polanyi principle and Hammond-Leffler postulate. The results confirm that asynchronicity is an important factor to consider, as it affects the reorganization energy and exothermicity of the reaction.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Biochemistry & Molecular Biology
Ivana Antol, Zoran Glasovac, Davor Margetic
Summary: Density functional calculations were used to study the 1,3-dipolar cycloadditions of azides with guanidine. The results suggest that the reaction through pathway (a) has a higher energy barrier, while the reaction through pathway (b) can proceed under milder conditions. The introduction of substituents can enhance the cycloaddition reactivity of the azides.
Article
Chemistry, Physical
Cesar Barrales-Martinez, Jorge Martinez-Araya, Pablo Jaque
Summary: The study provides a deeper understanding of 1,3-dipolar cydoadditions through three chemical reactivity models, confirming the fulfillment of the BEP principle. As the activation energy increases, reactions shift from HOMO-controlled to LUMO-controlled, supporting the BEP principle. The distortion/interaction and reaction force analysis show that structural rearrangements primarily drive activation barriers in these reactions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Organic
Wei Li, Hengyuan Li, Jie Qiu, Zhenhui Wang, Xiaofeng Li, Ying-Ming Pan, Cheng Hou, Huaifeng Li
Summary: In this study, an efficient method for synthesizing 2-pyrazolines with a CF3- and alkyne-substituted quaternary carbon center is reported. This methodology offers high functional group compatibility, easily accessible reagents, and broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Joaquin Plumet
Summary: The 1,3-dipolar cycloadditions of nitrile oxides have been widely used in synthetic organic chemistry as a powerful tool. The cycloadducts arising from the cycloadditions of nitrile oxides to alkenes and alkynes are valuable synthetic intermediates due to their capacity to mask other functionalities, with the beta-hydroxy ketone functionality being an illustrative example.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Muhammad Sohail, Fujie Tanaka
Summary: This account describes the strategies for the synthesis of functionalized spirooxindole polycycles, including enantiomerically enriched forms, that we have developed and reported. The syntheses of these complex molecules were accomplished in a few steps starting from relatively simple oxindole derivatives and other reactants. Organocatalytic reactions involved in kinetic resolution or in dynamic kinetic transformation led to the formation of products with high diastereoand/or enantioselectivities.
Article
Chemistry, Organic
Natalia Labadie, Silvina C. Pellegrinet
Summary: A DFT study was conducted to investigate the Diels-Alder reactions of vinyl-boronic acid pinacol ester, allenylboronic acid pinacol ester, methyl acrylate, and methyl 2,3-butadienoate with cyclopentadiene. The competitive mechanisms of the carboxylic esters were fully explored and yielded similar results to previous studies on organoboron compounds. Additionally, the reactivity and selectivity patterns were accurately reproduced. The distortion/interaction-activation strain energy model analysis provided a rationale to explain the experimental outcome of the studied [4 + 2] cycloadditions. The regioselectivity of the allenyl compounds and the relative reactivity of the boronic and carboxylic esters are attributed to electronic effects arising from orbital overlap and correlating with the energies of the vacant orbitals of the dienophiles, while the lower reactivity of the allenes compared to vinyl compounds may be due to the distortion of the dienophiles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Biochemistry & Molecular Biology
Hua Zhao, Yufen Zhao
Summary: Multicomponent reactions (MCRs) have become indispensable tools for organic chemists worldwide, finding extensive utility in the synthesis of complex natural products, heterocyclic molecules with significant bioactivity, and pharmaceutical agents. The multicomponent one-pot 1,3-dipolar cycloaddition reaction is highly favored in terms of green synthesis due to its high step- and atom-economies, remarkable product diversity, as well as excellent efficiency and diastereoselectivity.
Article
Chemistry, Organic
Francisco V. Gaspar, Marcelo F. M. F. Azevedo, Leonardo S. A. Carneiro, Samuel B. Ribeiro, Pierre M. Esteves, Camilla D. Buarque
Summary: This study reports the synthesis of new 4-acyl-1,2,3-triazoles through metal-free and solvent-free cycloaddition reactions, achieving high yields. The reaction mechanism for the synthesis of 4-acyl-1,2,3-triazoles was proposed based on experimental and theoretical data.
Article
Chemistry, Physical
Meylin Bocalandro, Juan J. Gonzalez Armesto, Luis A. Montero-Cabrera, Marco Martinez Gonzalez
Summary: The 1,3 dipolar cycloaddition reactions between munchnones and alkenes offer a convenient method for synthesizing substituted pyrroles, which are important structural motifs in pharmaceutical and material science research. The factors influencing the regioselectivity of these reactions are not well understood. In this study, we investigated 14 reactions involving munchnones, alkenes, and alkynes using various analytical methods. Our results show that the prediction of the major regioisomer based on non-covalent interaction energies or DFT descriptors is inaccurate, while considering local softness pairing and steric effects can provide reliable predictions for the major reaction product.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Organic
Kohei Fuchibe, Kazuki Sakon, Kyosuke Suto, Reo Eto, Sho Nakazono, Junji Ichikawa
Summary: In this study, a regioselective [2+3] cycloaddition reaction of 1,1-difluoroallenes with nitrile oxides and imine oxides was achieved in the presence of an AuCl catalyst. The reaction produced (E)-4-alkylidene-5,5-difluoroisoxazolines and -isoxazolidines in a regioselective and diastereoselective manner using aurated difluoroallylic cation intermediates. The synthesized 5,5-difluoroisoxazolines could be easily aromatized into 5-fluoroisoxazoles through dehydrofluorination or allylic fluorine substitution.
Article
Chemistry, Organic
Ahmed G. Taha, Elghareeb E. Elboray, Yusuke Kobayashi, Takumi Furuta, Hussien H. Abbas-Temirek, Moustafa F. Aly
Summary: The 1,3-dipolar cycloaddition reactions of 2- and 3-nitrobenzaldehydes with 2-aminomethylpyridine and ethyl (2E)-2-cyano-3-(4-nitrophenyl)prop-2-enoate were found to selectively yield endo-cycloadducts as the sole products under various reaction conditions. However, 4-nitrobenzaldehyde behaved differently, producing a mixture of endo- and exo'-cycloadducts. The reaction is solvent- and temperature-dependent, and both endo- and exo'-cycloadducts were synthesized in an excellent regio-, stereo-, and chemoselective fashion. Retro-1,3-dipolar cycloadditions of the endo-cycloadducts were conducted, and mechanistic studies were carried out to support proposed mechanisms.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Nikita A. Kaminskiy, Ekaterina E. Galenko, Mariya A. Kryukova, Mikhail S. Novikov, Alexander F. Khlebnikov
Summary: This study discovered that alpha-diazopyrroles selectively react with enamines at room temperature to produce organic compounds, which can be used for the synthesis of functionalized heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yipeng Zhou, Hongwei Zhou, Jianfeng Xu
Summary: A highly selective [3+2] cycloaddition reaction was achieved using a chiral catalyst, resulting in the synthesis of enantioenriched bicyclic pyrazolidinones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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)