Review
Chemistry, Multidisciplinary
G. Mahantesh, Deepika Sharma, Rambabu Dandela, Vasudevan Dhayalan
Summary: This article reviews the synthesis and properties of N-heterocyclic olefins (NHO), as well as their applications as catalysts in organic synthesis. NHOs display electron-rich and polar characteristics, as well as strong basicity, making them highly promising catalysts with great chemical potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hyunho Kim, Minseop Kim, Hayoung Song, Eunsung Lee
Summary: The synthesis of ambiphilic N-heterocyclic carbene ligand indol-2-ylidene (IdY, A) was described, along with its ambiphilicity and synthetic utility. Experimental and computational studies showed that IdY lies between CAAC-5 and CAArC, with copper complexes capable of carboboration of terminal alkynes with high regioselectivity and good yields within 30 minutes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Nanoscience & Nanotechnology
Zichao Wei, Kayceety Mullaj, Aleisha Price, Kecheng Wei, Qiang Luo, Srinivas Thanneeru, Shouheng Sun, Jie He
Summary: This study presents a method for preparing metal nanoparticles (NPs) using polymer N-heterocyclic carbenes (NHCs) as surface ligands. The results demonstrate that polymer NHC-modified AgNPs exhibit excellent resistance to oxidative etching and enhanced peroxidase activity.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Planer, Jenni Frosch, Marvin Koneczny, Damian Trzybinski, Krzysztof Wozniak, Karol Grela, Matthias Tamm
Summary: This study explores the use of lithium complexes with weakly coordinating borate moieties for the preparation of silver(I) or copper(I) WCA-NHC complexes. Reactions in different solvents and with different metals are investigated, revealing various transformations during the process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Changpeng Chen, Feng-Shou Liu, Michal Szostak
Summary: The discovery of NHCs as ancillary ligands has greatly improved catalytic processes, with BIAN-NHC ligands in particular showing enhanced reactivity due to combinations of electronic and steric properties. The development of BIAN-NHC ligands has led to major advancements in catalysis and offers a practical alternative to classical NHCs.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Yaping Cheng, Geoffrey Gontard, Abderrahim Khatyr, Michael Knorr, Hani Amouri
Summary: Luminescent N-heterocyclic carbene chloride copper (I) complexes incorporating pyrene chromophore (1-Pyrenyl-NHC-R)-Cu-Cl with different substituents (methyl or naphthyl) were synthesized and characterized. X-ray diffraction confirmed the formation of the target compounds. These compounds exhibited blue emission in both solution and solid-state at room temperature, with comparable or higher quantum yields than the parent pyrene molecule. Notably, the quantum yield was increased by almost two-fold by replacing the methyl group with a naphthyl group. These compounds show potential for applications in optical displays.
Article
Chemistry, Multidisciplinary
Laura Hippolyte, Omar Sadek, Salem Ba Sowid, Alexandre Porcheron, Nathalie Bridonneau, Sebastien Blanchard, Marine Desage-El Murr, David Gatineau, Yves Gimbert, Dimitri Mercier, Philippe Marcus, Clement Chauvier, Corinne Chaneac, Francois Ribot, Louis Fensterbank
Summary: In this paper, a straightforward synthesis method for NHC-coated gold nanoparticles (NHC-AuNPs) is reported. The commercially available gold(I) precursor is treated with an easy-to-synthesize NHC-BH3 reagent, serving as both the reducing agent and the source of surface ligands. The strategy allows efficient control over the nucleation and growth of gold particles, resulting in a wide range of particle size variation from 4.9±0.9 to 10.0±2.7 nm. The NHC-AuNPs obtained exhibit narrow size distributions, stability over months, and do not require extensive purification or size-selectivity techniques.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuan-Yuan Xu, Zhong-Hua Gao, Cao-Bo Li, Song Ye
Summary: The enantioselective alpha-oxidative coupling of enals with carboxylic acids was achieved by umpolung of an NHC-bound enolate with an iodine(III) reagent. The reaction produced alpha-acyloxyl-beta,gamma-unsaturated esters in good yields, with high regio- and enantioselectivities. The reaction involved the formation of an enol iodine(III) intermediate from the enolate with iodosobenzene, which changed the polarity of the enal's alpha-carbon from nucleophilic to electrophilic and facilitated the subsequent carboxylate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zi-Jing Zhang, Yu-Hua Wen, Jin Song, Liu-Zhu Gong
Summary: The study developed an efficient KR and DyKAT method using N-heterocyclic carbene (NHC)/copper cooperative catalysis, resulting in highly enantioenriched derivatives and products with high structural diversity. Mechanistic studies indicated that NHC can regulate the catalytic activity of the copper catalyst, enabling the switch of chemical selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Soumen Barik, Sayan Shee, Soumik Das, Rajesh G. Gonnade, Garima Jindal, Subrata Mukherjee, Akkattu T. Biju
Summary: This study describes the atroposelective synthesis of N-aryl succinimides with axially chiral C-N bonds catalyzed by N-heterocyclic carbenes, achieving good yields and ee values. Preliminary investigations were also conducted on the rotation barrier for the C-N bond, temperature dependence, and detailed DFT studies on the mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Simiao Zhang, Xiaoxue Wang, Li-Li Han, Jibin Li, Zheng Liang, Donghui Wei, Ding Du
Summary: Atropisomers bearing multiple stereogenic axes have become increasingly important in material science, pharmaceuticals, and catalysis. However, the construction of multi-axis atropisomers with high stereoselectivity remains rare and challenging. In this study, a new class of 1,2-diaxially chiral triaryl alpha-pyranones was successfully synthesized in a single-step reaction, demonstrating broad substrate scope and excellent stereo-control. The success of this reaction can be attributed to the rational design of structurally matched reaction partners and the careful selection of the asymmetric catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chun-Lin Zhang, Yuan-Yuan Gao, Hai-Ying Wang, Bang-An Zhou, Song Ye
Summary: An NHC-catalyzed de novo synthesis method for axially chiral benzothiophene/benzofuran-fused biaryls has been reported, providing a convenient and efficient access to these compounds with high enantioselectivities. The method also works well for the synthesis of tetra-ortho-substituted biaryls, addressing an unsolved problem in the field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Thomas Scattolin, Giovanni Tonon, Eleonora Botter, Sebastien G. Guillet, Nikolaos V. Tzouras, Steven P. Nolan
Summary: The review focuses on the design of gold-based synthons that enable the synthesis of target complexes through simple steps under mild conditions. Mechanistic aspects of their synthesis and reactivity, as well as applications as efficient pre-catalysts, antitumor agents, and photo-emissive materials, are discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Li-Cheng Xu, Xin Li, Miao-Jiong Tang, Luo-Tian Yuan, Jia-Yu Zheng, Shuo-Qing Zhang, Xin Hong
Summary: The description of molecular stereostructure is crucial for the machine learning prediction of asymmetric catalysis. A spherical projection descriptor of molecular stereostructure (SPMS) is introduced to accurately represent the molecular van der Waals surface, demonstrated using chiral phosphoric acid as an example and applied in the asymmetric thiol addition to N-acylimines dataset from Denmark. Additionally, SPMS descriptor features a color-coded diagram for easy chemical interpretation of the steric environment.
Article
Multidisciplinary Sciences
Yi-Kang Xing, Xin-Ran Chen, Qi-Liang Yang, Shuo-Qing Zhang, Hai-Ming Guo, Xin Hong, Tian-Sheng Mei
Summary: Alpha-pyridones and alpha-pyrones are common structural motifs in natural products and biologically active compounds. This study reports an oxidant-free Rh-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes, providing alpha-pyridones and cyclic imidates through divergent pathways with excellent regioselectivities.
NATURE COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Shuo-Qing Zhang, Xin Hong
Summary: Transition-metal-catalyzed C-O bond activation is a crucial strategy in organic synthesis, where catalyst-induced stereochemistry and solvent polarity play significant roles in controlling the activation selectivity. With the advances in mechanistic understanding and collaboration between computational and experimental studies, precise control over activation reactions can be achieved.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Li-Cheng Xu, Shuo-Qing Zhang, Xin Li, Miao-Jiong Tang, Pei-Pei Xie, Xin Hong
Summary: The article introduces a standardized database containing detailed information of asymmetric hydrogenation experiments, which is used for developing predictive machine learning models for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Li-Cheng Yang, Lu-Jing Zhu, Shuo-Qing Zhang, Xin Hong
Summary: Data-driven approaches have proven to be effective in bridging the gap between mechanistic understanding and synthetic prediction in organic synthesis. This article discusses the implementation of mechanistic knowledge in machine learning models for accurate predictions of reactivity and selectivity. The authors emphasize the importance of comprehensive computational databases and the combination of computational statistics and physical organic descriptors in building structure-performance models. They also highlight the significance of integrating mechanistic knowledge and machine learning in pushing the limits of reaction performance prediction in organic chemistry.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dan-Dan Zhai, Shuo-Qing Zhang, Si-Jun Xie, Rong-Kai Wu, Feng Liu, Zhen-Feng Xi, Xin Hong, Zhang-Jie Shi
Summary: Splitting N-2 is an important and challenging chemical transformation, but most methods rely on strong reducing agents which are incompatible with functionalizing agents. This study demonstrates an efficient and sustainable N-2 splitting using (n-Bu)(4)NBr as a catalyst to produce metal nitrides under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Shuo-Qing Zhang, Li-Cheng Xu, Shu-Wen Li, Joao C. A. Oliveira, Xin Li, Lutz Ackermann, Xin Hong
Summary: In recent years, there has been a significant increase in the application of machine learning in the field of chemistry, showcasing the potential of data-driven prediction of synthesis performance. This minireview summarizes the latest techniques and designs in synthetic performance prediction, emphasizing the importance of incorporating chemical knowledge in machine learning. It hopes to inspire chemists to revisit the digitalization and computerization of organic chemistry principles.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qing An, Yang-Yang Xing, Ruihua Pu, Menghui Jia, Yuegang Chen, Anhua Hu, Shuo-Qing Zhang, Na Yu, Jianbo Du, Yanxia Zhang, Jinquan Chen, Weimin Liu, Xin Hong, Zhiwei Zuo
Summary: The importance of alkoxy radicals in cerium-catalyzed C-H functionalization reactions has been confirmed and the involvement of chlorine radicals has been ruled out. The study also emphasizes the influence of the relative ratio of alcohol to cerium on the reaction selectivity. Furthermore, the selectivity of alkoxy radical generation and the regulatory role of back-electron transfer have been analyzed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yan-Yu Li, Shuo-Qing Zhang, Xin Hong
Summary: The concerted mechanism of thermal BBr3-mediated [2+2] carbonyl-olefin cycloaddition is studied using density functional theory calculations. The reaction follows an asynchronous concerted [2+2] cycloaddition mechanism due to the proximity of carbocation-oxyanion in the transient zwitterionic structure. Solvent effects can change the reaction to a stepwise mechanism, emphasizing the importance of zwitterion stability. Two mechanistic classifications are developed based on substrates with varied substituents and Lewis acids, focusing on manipulating the stability of positive carbocation and negative oxyanion in the transient zwitterionic species.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Si-Jun Xie, Rong-Kai Wu, Yi-Fei Huang, Hao-Lin Chen, Shuo-Qing Zhang, Feng Liu, Xin Hong, Dan-Dan Zhai, Zhang-Jie Shi
Summary: This study reports the first example of dinitrogen insertion into an aliphatic Csp3-H bond on the ligand scaffold of a 1,3-propane-bridged dititanium complex. Mechanistic investigations revealed the intramolecular synergistic effect of two Ti centers at a C-N bond-forming step. This strategy provides an efficient route for the future synthesis of aliphatic amines directly from N2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Shu-Wen Li, Li-Cheng Xu, Cheng Zhang, Shuo-Qing Zhang, Xin Hong
Summary: We report a knowledge-based graph model that embeds digitalized steric and electronic information to achieve predictive modeling of synthetic transformation. A molecular interaction module is developed to learn the synergistic influence of reaction components. The model demonstrates excellent predictions of reaction yield and stereoselectivity, with good extrapolative ability and atomic-level interpretation.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Chaoyue Zhao, Rongkai Wu, Shuoqing Zhang, Xin Hong
Summary: The current study aims to determine the most precise theoretical method for optimizing the geometry of transition metal-dinitrogen complexes. Seven density functional methods were selected and applied to forty-two transition metal-dinitrogen compounds. The results indicate that M06, M06-L, and TPSSh-D3(BJ) are the most reliable methods for optimizing the geometry of these complexes, with M06-L being the best.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Zi-Chao Wang, Yan-Yu Li, Shuo-Qing Zhang, Xin Hong, Shi-Liang Shi
Summary: This article reports a highly efficient nickel catalyst for the arylation of sterically hindered primary and secondary amines with aryl chlorides or phenol derivatives, enabled by an unsymmetric N-heterocyclic carbene ligand. The method is general, efficient, and scalable, providing excellent yields of various sterically demanding anilines under mild conditions. Computational studies suggest that the unsymmetric bulky and flexible N-heterocyclic carbene ligand plays a critical role in balancing the oxidative addition and reductive elimination steps.
Article
Chemistry, Physical
Zhen-Yao Dai, Shuo-Qing Zhang, Xin Hong, Pu-Sheng Wang, Liu-Zhu Gong
Summary: In this study, a robust and practical FeCl3/HCl photocatalytic system was identified, which allows efficient functionalization of ubiquitous C(sp(3))H bonds including alkylation, oxidation, chlorination, fluorination, amination, alkynylation, and sulfonylation with high turnover number (TON).
Article
Chemistry, Multidisciplinary
Dan-Dan Zhai, Shuo-Qing Zhang, Si-Jun Xie, Rong-Kai Wu, Feng Liu, Zhen-Feng Xi, Xin Hong, Zhang-Jie Shi
Summary: This study presents a novel method for N-2 splitting using (n-Bu)(4)NBr as a catalyst to facilitate the process on a Mo(III) platform. Experimental and theoretical investigations suggest that X- anions play a crucial role in inducing the catalysis at the early stage, leading to the generation of a catalytically active species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
