Article
Chemistry, Organic
Han-Peng Pan, Zhi-Qiang Zhu, Zong-Wang Qiu, Hong-Fu Liu, Jiong-Dong Ma, Bao Qiong Li, Na Feng, Ai-Jun Ma, Jin-Bao Peng, Xiang-Zhi Zhang
Summary: This study presents an efficient method for dearomatization of 2,3-disubstituted indoles to access diverse indolimines with quaternary carbon centers and tetrasubstituted allenes through 1,8-addition of (aza)-para-quinone methides. The products can be obtained in good yields (up to 99%) with separability of isomers, diversified product transformations, and easy scale-up potential, showcasing the method's applicability.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Physical
Mercedes Zurro, Aitor Maestro
Summary: This paper reviews the recent literature on the catalytic methodologies for the derivatization of aza-QM, including organocatalytic and organometallic approaches. The review analyzes various catalytic systems, involving chiral NHC carbenes, phosphoric acids, phosphoramidites, phosphine, copper, and palladium catalysis, showcasing their applicability for the synthesis of a diverse array of N-containing compounds, many of which exhibit biological activity.
Article
Chemistry, Organic
Xiao Lin, Boming Shen, Ziyang Wang, Yuyu Cheng, Xuling Chen, Pengfei Li, Peiyuan Yu, Wenjun Li
Summary: In this study, an asymmetric organocatalytic reaction was developed for the first time, enabling the remote 1,10-addition of alkynyl indole imine methides generated in situ from alpha-(6indolyl) propargylic alcohols with thiazolones. The reaction yielded axially chiral tetrasubstituted allenes featuring vicinal sulfur-containing quaternary carbon stereocenters, with high yields and excellent stereoselectivities. The scalability of the reaction and the chemical transformations of the 1,10-adduct were also investigated. Control experiments and DFT calculations were conducted to elucidate the reaction mechanism.
Article
Chemistry, Multidisciplinary
Kai Li, Shengli Huang, Tianyu Liu, Shiqi Jia, Hailong Yan
Summary: We demonstrated an organocatalytic asymmetric dearomatizing hetero-Diels-Alder reaction of benzene derivatives, which allows the synthesis of diverse stereochemically complex compounds and oxahelicenes. The high complexity and three-dimensionality of the products are crucial for their potential applications in materials science and drug discovery.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Rupashri Dash, Sudhir Kumar Hota, Sandip Murarka
Summary: We describe an efficient higher order conjugate addition reaction of azauracils to substituted para-quinone methides (p-QMs) mediated by triethylamine, forming previously unknown diarylmethane scaffolds through C-N bond formation. This protocol offers mild conditions, high atom economy, broad scope, and allows convenient access to biologically relevant new chemical entities (NCEs) consisting of p-QM and azauracil hybrids in good to excellent yields.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Meiwen Liu, Boming Shen, Chang Liu, Peiyuan Yu, Pengfei Li
Summary: In this study, an organocatalytic asymmetric synthesis of chiral tetraarylmethanes was reported. Through the use of a chiral phosphoric acid catalyst, chiral tetraarylmethanes were synthesized from racemic tertiary alcohols. The method involved stereoselective 1,8-conjugate addition reactions, yielding the tetraarylmethanes with high enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Jian-Qiang Zhao, Wen-Jie Wang, Shun Zhou, Qi-Lin Xiao, Xi-Sha Xue, Yan-Ping Zhang, Yong You, Zhen-Hua Wang, Wei-Cheng Yuan
Summary: An unprecedented N-alkylation of 3-nitroindoles with para-quinone methides was developed for the first time. Using potassium carbonate as the base, a wide range of structurally diverse N-diarylmethylindole derivatives were obtained with moderated to good yields via the protection group migration/aza-1,6-Michael addition sequences. The reaction process was also demonstrated by control experiments.
Article
Chemistry, Multidisciplinary
Shaukat Ali, Muhammad Israr
Summary: This paper highlights the recent studies on the organocatalytic asymmetric dearomatization of nonactivated arenes, obtaining complex stereoisomeric products by harnessing the reactivity of chiral vinylidene ortho-quinone methides (VQMs) generated in situ.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Kavyashree Kuppayya Gond, Mahagundappa Rachappa Maddani
Summary: In this study, isochroman-1,4-diones and addition products were selectively synthesized through KOBu-Catalyzed addition of sulfonylphthalides to p-quinone methides. It is noteworthy that isochroman-1,4-diones were obtained via an unprecedented oxidative annulation pathway. The research highlights the broad substrate scope, high yields, shorter reaction time, and mild reaction conditions. Furthermore, some addition products can be transformed into functionalized heterocyclic molecules. Additionally, the scalability experiment demonstrates the practical feasibility of preparing isochroman-1,4-diones in larger scale reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Applied
Deyuan Meng, Jing He, Woojin Yoon, Hoseop Yun, Jung Tae Han, Jaesook Yun
Summary: In this study, the catalytic 1,6-addition of chiral alkyl copper nucleophiles generated from borylalkenes and a copper-hydride catalyst was successfully conducted under mild conditions. The controlled chemo- and stereoselectivity played a crucial role in the reductive coupling process, resulting in efficient synthesis of asymmetric 1,6-adducts of p-quinone methides through multicomponent and catalytic tandem reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Chandan Gharui, Chandrakanta Parida, Subhas Chandra Pan
Summary: An organocatalytic asymmetric addition reaction of aromatic alpha-cyanoketones to in situ-generated o-quinone methides was successfully developed, leading to the synthesis of 3,4-dihydrocoumarin and tetrasubstituted chroman products. The desired products were obtained with high enantio- and diastereoselectivities under 10 mol % catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Zhiguang Zhang, Xiaoyu Tan, Ao Sui, Bingzhu Zhang, Yong Zhang
Summary: A DBU-catalyzed 1,6-addition reaction of quinazolinones and quinolones with para-quinone methides under mild conditions is reported. Diarylmethane compounds functionalized with quinazolinones and quinolones were obtained in good yields (41-95%) with DBU as catalyst.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Applied
Navpreet Kaur, Priyanka Singh, Prabal Banerjee
Summary: An efficient protocol for the synthesis of spiro-imidazolidinone-cyclohexadienones from p-quinone methides and dialkyloxy ureas is reported, showing good functional group tolerance and providing a straightforward method for accessing the desired compounds. Additionally, the debenzylation of spiroimidazolidinones to give N-hydroxycyclic ureas has been demonstrated in follow-up chemistry.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Guangmiao Wu, Tao Li, Fuhai Liu, Yulong Zhao, Shiqiang Ma, Shouchu Tang, Xingang Xie, Xuegong She
Summary: An efficient thiourea-catalyzed 1,6-conjugate addition of indoles to para-quinone methides (p-QMs) was developed, where p-QMs were activated by a weak hydrogen-bond effect. The reaction features mild conditions and a wide substrate scope, allowing for the synthesis of a series of C-3 bisaryl methine substituted indoles in high yield.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Qinfang Yan, Yi Jiang, Xianheng Song, Guoqing Lu, Qianzhong Zhang, Zhibo Du, Albert S. C. Chan, Yong Zou
Summary: A facile and practical approach for the synthesis of natural coumestans and derivatives starting from 2',4'-dihydroxyl-3-arylcoumarins has been developed. The process involves a sequential intramolecular dehydrogenation/oxa-Michael reaction efficiently promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene at 40 degrees C under metal- and ligand-free conditions with good functional group compatibility.
JOURNAL OF ORGANIC CHEMISTRY
(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
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, 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
Chemistry, Organic
Qi Yang, Junxue Bai, Han Yang, Yang Yao, Yingming Yao, Jianwei Sun, Song Sun
Summary: A [Cp*IrCl2](2)-catalyzed amidocarbonation of olefins with sulfoxonium ylides has been developed, enabling the efficient generation of diverse biologically important isoindolin-1-ones under mild reaction conditions. Mechanistic studies revealed that this cascade reaction proceeds through amino-iridation of the olefin unit to form an iridacycle, followed by formal migratory insertion with sulfoxonium ylides. This newly developed method offers broad substrate scopes and operational simplicity.
Article
Chemistry, Organic
Hongling Xie, Lei Chen, Zhengyu Han, Zhenkun Yang, Jianwei Sun, Hai Huang
Summary: Ligand-directed divergent synthesis (LDS) is a powerful method for the efficient preparation of structurally diverse organic molecules without the need for tedious substrate modifications. In this study, we demonstrate the realization of 3,4-, 1,2-, and 1,4-cyclization of benzo[d]isothiazole-1,1-dioxide-fused azadienes (BDAs) through LDS, leading to the formation of tetrahydro-2H-pyrans, oxazinanes, and tetrahydro-2H-1,5-oxazocines, respectively. By employing phosphinooxazoline (PHOX) ligands, we have also developed a [4 + 2] cycloaddition between BDAs and substituted 2-alkylidenetrimethylene carbonates, enabling the synthesis of multi-substituted chiral tetrahydro-2H-pyrans with high yields and excellent enantio-, diastereo-, and regioselectivities.
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)
