Article
Biochemistry & Molecular Biology
Domenique Herbstritt, Pooja Tomar, Thomas Braun
Summary: In this study, the greenhouse gas SF(5)CF(3) was photochemically activated with SIMes to generate various organic compounds. Additionally, the photochemical activation of SF(5)CF(3) in the presence of triphenylphosphine was also investigated.
Article
Chemistry, Multidisciplinary
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis has the potential to achieve oxidative and oxygenative transformations, generating various NHC-bound intermediates and enabling non-umpolung processes through the activation of carbon atoms and heteroatoms. This review aims to discuss the recent developments in the field of oxidative NHC catalysis since 2014, with a focus on pivotal intermediates and their mechanistic involvement. More details can be found in the review article by C. De Risi and co-workers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis enables oxidative and oxygenative transformations, producing various NHC-bound intermediates and facilitating non-umpolung processes by activating carbon atoms and heteroatoms. This review discusses the developments in the literature on oxidative NHC catalysis since 2014, with a specific focus on pivotal intermediates and their mechanistic involvement.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Bang-An Zhou, Chun-Lin Zhang, Song Ye
Summary: Researchers have developed an NHC-catalyzed benzannulation reaction for the synthesis of benzotrifluorides using enals and beta-trifluoromethylenones. This reaction involves a [4 + 2] annulation/lactonization/decarboxylation/oxidative aromatization cascade catalyzed by NHC. The reaction shows mild conditions, excellent functional group compatibility, and exclusive regioselectivity, resulting in the formation of multi-substituted benzotrifluorides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
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)
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)
Review
Chemistry, Physical
Guangjin Zhen, Kai Jiang, Biaolin Yin
Summary: Dearomative reactions enable the concise assembly of highly functionalized three-dimensional molecules by disrupting the aromaticity of starting materials. N-heterocyclic carbenes (NHCs) have emerged as powerful catalysts for dearomatization reactions, allowing for the construction of natural product and drug skeletons. This overview summarizes the progress in NHC-catalyzed dearomative reactions, classifying the reactions by modes and categories of intermediates and providing representative mechanisms.
Article
Chemistry, Multidisciplinary
Tingting Li, Chengli Mou, Puying Qi, Xiaolin Peng, Shichun Jiang, Gefei Hao, Wei Xue, Song Yang, Lin Hao, Yonggui Robin Chi, Zhichao Jin
Summary: A catalytic atroposelective cycloaddition reaction between thioureas and ynals has been developed, enabling the establishment of C-N axial chirality with excellent optical purities. The resulting axially chiral thiazine derivative products contain multiple functional groups and are suitable for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jin Hyun Park, Sun Bu Lee, Byeong Jun Koo, Han Yong Bae
Summary: A water-accelerated, N-heterocyclic carbene (NHC)-catalyzed aza-Michael addition reaction was reported for the synthesis of beta-aminosulfonyl fluorides, key components of the SuFEx reaction. Water as a reaction medium significantly enhanced the reaction rate and demonstrated late-stage ligation with bioactive molecules.
Article
Multidisciplinary Sciences
Guanjie Wang, Min Zhang, Yezhi Guan, Ye Zhang, Xianfang Hong, Chenlong Wei, Pengcheng Zheng, Donghui Wei, Zhenqian Fu, Yonggui Robin Chi, Wei Huang
Summary: A novel prochiral fluorinated oxindanyl 1,3-diketone has been developed for asymmetric desymmetrization, leading to the generation of enantioenriched organofluorines with excellent yields and diastereoselectivities. Switchable stereoselectivity was achieved by exchanging fluorinated methyl groups to fluorine, and the mechanism and origin of stereoselectivity were studied by DFT calculations. Furthermore, some of the prepared organofluorines exhibited competitive antibacterial activities.
Review
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Bo Han, Jun-Long Li
Summary: In recent years, the N-heterocyclic carbene (NHC) organocatalysis field has seen the emergence of long-awaited single-electron transfer (SET) reactions, providing opportunities to develop new catalytic modes and useful synthetic methods.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Daniele Ragno, Carmela De Risi, Alessandro Massi, Graziano Di Carmine, Sofia Toldo, Costanza Leonardi, Olga Bortolini
Summary: A novel NHC-promoted synthesis method for biologically active isosorbide imidates was described. The method allows the easy synthesis of different benzothiazole products by using accessible aldimines and oxidative conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Biochemistry & Molecular Biology
Camilo Morales-Manrique, Edwin A. Baquero, James Guevara-Pulido
Summary: In recent years, N-heterocyclic carbenes (NHCs) have been recognized as versatile organocatalysts for the activation of aldehydes, leading to the production of 3,4-dihydropyran-2-ones and related derivatives. This review provides an overview of the organocatalytic processes involving NHCs in synthesizing these compounds over the past eight years. These processes utilize various substrates, catalysts, and reaction conditions, mainly focusing on [4+2] and [3+3] cycloadditions to generate the desired skeleton with biological activity and multiple stereocenters. The resulting products can be scaled up and further modified for potential applications in the field of biology.
Article
Chemistry, Organic
Jindian Duan, Pui Ying Choy, Kin Boon Gan, Fuk Yee Kwong
Summary: A general protocol for N-difluoromethylation of aniline derivatives using commercially available ethyl bromodifluoroacetate as a difluorocarbene source is developed, which exhibits notable operational simplicity, wide functional group tolerance, and good-to-excellent product yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
En Li, Jiean Chen, Yong Huang
Summary: The Michael reaction is an important method for preparing functional molecules with a β-stereogenic center. However, the enantioselective seleno-Michael addition is still poorly explored. In this study, a highly enantioselective Michael addition reaction of alkyl selenols to enones was reported, introducing a Se atom asymmetrically to an electron-deficient double bond. A chiral bifunctional N-heterocyclic carbene (NHC)/thiourea catalyst was developed and showed remarkable selectivity in delivering chiral β-seleno ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yong Wang, Yuxuan Li, Lei Wang, Shengtao Ding, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: In this study, a new method for efficient construction of gem-diboryl compounds with hetero-substituted carbon centers was developed. This method involves the alpha-dihydroboration of heteroalkynes and is a practical and atom-economic alternative to the conventional multistep synthetic strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xiu-Qin Dong, Xuanliang Yang, Gang Liu, Xun Xiang, Dezheng Xie, Jinyu Han, Zhengyu Han
Summary: Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of alpha-substituted alpha,beta-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral alpha-substituted phosphine hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%-99% yields, 84%->99% ee). This method features a cheap transition metal nickel catalytic system, high functional group tolerance, wide substrate scope generality, and excellent enantioselectivity. A plausible catalytic cycle was proposed for this asymmetric hydrogenation according to the results of deuterium-labeling experiments.
Article
Chemistry, Organic
Zhengyu Han, Wenlong Wang, Han Zhuang, Jie Wang, Cheng Wang, Jianhao Wang, Hai Huang, Jianwei Sun
Summary: This article describes an organocatalytic enantioselective formal hydro-arylation of 2-vinyl indoles for the synthesis of enantioenriched 2,3'-bis(indolyl)methanes bearing a quaternary carbon stereocenter. The reaction conditions are mild, the catalyst loading is low, and the efficiency and enantioselectivity are excellent. The resulting products exhibit promising anticancer activity.
Article
Multidisciplinary Sciences
Xuefeng Tan, Qingli Wang, Jianwei Sun
Summary: The authors have successfully achieved catalytic asymmetric bromocyclization processes induced by weak ion-pairing interaction under electrochemical conditions. This overcomes the challenges related to solvent polarity and electrolyte interference, allowing for electricity-driven asymmetric catalysis.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kristy W. K. Lam, Joe H. C. Chau, Eric Y. Yu, Feiyi Sun, Jacky W. Y. Lam, Dan Ding, Ryan T. K. Kwok, Jianwei Sun, Xuewen He, Ben Zhong Tang
Summary: In this study, a phosphate group was introduced as a cancer-specific biomarker of alkaline phosphatase (ALP) on a photosensitizer (PS) with aggregation-induced emission (AIE) for cancer cell imaging and therapy. The phosphate group on the PS is selectively hydrolyzed by ALP in high ALP expressing cancer cells, leading to aggregation and fluorescent response. Furthermore, fluorescence-guided photodynamic therapy (PDT) was achieved by using the aggregates of PS with strong reactive oxygen species (ROS) generation efficiency under white light irradiation.
Article
Chemistry, Organic
Chenchen Li, Qi Qin, Aocong Guan, Wen Yang, Wanxiang Zhao
Summary: We present a general and efficient transition-metal-free C-C bond cross-coupling reaction of (hetero)-aryl ethers and diarylmethanes via C-(sp(2))-O bond cleavage. The coupling reactions mediated by KHMDS demonstrated high efficiency, broad substrate scope, and good functional group tolerance. The robustness and practicality of this protocol were further demonstrated by gram-scale preparation and diversified product derivatization.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shuxuan Liu, Ka Lok Chan, Zhenyang Lin, Jianwei Sun
Summary: This article reports the use of extended quinone methides with carbonyl and methide units distributed across two different rings as intermediates for asymmetric synthesis. By using suitable chiral phosphoric acids, the first asymmetric process involving such intermediates was achieved. These processes provide a rapid and highly enantioselective access to previously less accessible remotely chiral naphthols and naphthylamines. Control experiments and DFT calculations reveal important insights into the reaction mechanism, which likely involves the role of two phosphoric acid molecules in the enantiodetermining transition states. This work serves as a proof of concept for the exploitation of new types of extended quinone methides as versatile intermediates for asymmetric synthesis, offering a new platform for the efficient construction of remote benzylic stereogenic centers of aromatic compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Polymer Science
Yunfei Zuo, Ryan T. K. Kwok, Jianwei Sun, Jacky W. Y. Lam, Ben Zhong Tang
Summary: Recent advancements in aggregation-induced emission (AIE) macromolecular materials have received attention as potential antibacterial solutions, providing new approaches for treating multidrug-resistant infections and biofilms, as well as real-time monitoring and specific targeting of bacteria. This review discusses the three main categories of AIE macromolecular materials with antibacterial properties and their mechanisms and applications in antibacterial treatment, wound care, and protective equipment. It also highlights the potential for future developments and application directions of AIE-based antimicrobial materials.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Jianyu Zhang, Yujie Tu, Hanchen Shen, Jacky W. Y. Lam, Jianwei Sun, Haoke Zhang, Ben Zhong Tang
Summary: This study systematically illustrates the impacts of proximity effect and aggregation-induced emission (AIE) on luminescent behaviors of heterocyclic luminogens. The authors report a series of methylquinoxaline derivatives and reveal the energy level changes and coupling effects of the closely related (n,& pi;*) and (& pi;,& pi;*) states, which intrinsically regulate proximity effect and AIE behaviors. The results provide insights into the development of functional and responsive luminogens with AIE properties.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Liang Zhang, Shu-Cheng Wan, Jianyu Zhang, Meng-Jie Zhang, Qi-Chao Yang, Boxin Zhang, Wu-Yin Wang, Jianwei Sun, Ryan T. K. Kwok, Jacky W. Y. Lam, Hexiang Deng, Zhi-Jun Sun, Ben Zhong Tang
Summary: Covalent organic frameworks (COFs) have shown potential as porous materials for cancer phototherapy due to their unique characteristics. However, the aggregation-caused quenching effect and apoptosis resistance limit their effectiveness. This study demonstrated that linking AIEgens into COF networks was an effective strategy for inducing pyroptosis and enhancing antitumor immunity. The synergized system of AIE COF and αPD-1 effectively eradicated tumors and inhibited recurrence and metastasis in a tumor model.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Liang Zhang, An Song, Qi-Chao Yang, Shu-Jin Li, Shuo Wang, Shu-Cheng Wan, Jianwei Sun, Ryan T. K. Kwok, Jacky W. Y. Lam, Hexiang Deng, Ben Zhong Tang, Zhi-Jun Sun
Summary: This study presents a dual-inducer called COF-919, based on non-metallic AIEgen-based covalent organic frameworks, capable of triggering both pyroptosis and ferroptosis, resulting in enhanced anti-tumor immunity and inhibition of tumor growth and metastasis.
NATURE COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
Qicheng Yu, Jianyu Zhang, Jacky W. Y. Lam, Dong Yang, Jianwei Sun, Ben Zhong Tang
Summary: This research focuses on the development of room-temperature phosphorescent metal-organic frameworks (MOFs) with free heavy metal atoms, high quantum yields, and long lifetime. It is demonstrated that by ligand functionalization, heavy-atom-free CAU-10 MOFs with color-, lifetime-, and intensity-tunable intrinsic room temperature phosphorescence (RTP) can be achieved. The strong metal-organic coordination bond and firm anchoring of ligands make the MOFs show superior RTP performance and stability compared to pure organic ligands' crystals.
ACS MATERIALS LETTERS
(2023)
Article
Chemistry, Organic
Jie Wang, Run Yu, Cuicui Nian, Maoyan Liao, Zhengyu Han, Jianwei Sun, Hai Huang
Summary: Direct arylation of the benzylic C-(sp(3))-H bond is a straightforward strategy for the synthesis of multi-aryl methanes. In this paper, the first metal-free arylation of the C-(sp(3))-H bond in 3-methylindoles was developed, leading to the synthesis of diaryl- and triarylmethanes with two indole rings. The key intermediate in this reaction is the 3-indole imine methide. Water plays an important role in facilitating the crucial 1,3-proton transfer step and enhancing the reaction efficiency.
Article
Chemistry, Multidisciplinary
Jixing Li, Ming Fang, Maoyan Liao, Hongling Xie, Xiu-Qin Dong, Zhengyu Han, Jianwei Sun, Hai Huang
Summary: A tandem strategy has been developed for the synthesis of medium-sized heterocycles from oxetanes through the allylic amination/ring-opening of oxetanes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Huilin Zhan, Bin Chen, Biao Zhu, Xiang Li, Zhengyu Han, Jianwei Sun, Hai Huang
Summary: Based on a halopalladation strategy, we have developed a haloesterification reaction of propargylic amides to synthesize a diverse range of 5-(halomethylene)oxazolidine-2,4-diones. The reaction shows good yield and compatibility with various functional groups. Additionally, we have achieved the cyclizative dimerization of propargylic amides to produce bisoxazolidine-2,4-dione derivatives.
CHEMICAL COMMUNICATIONS
(2023)
