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, Multidisciplinary
Shiv Shankar Patel, Dileep Kumar, Chandra Bhushan Tripathi
Summary: This research addresses the generation of alkyl radicals under mild conditions through photoinduced Brönsted acid catalysis. The optimized protocol does not require organic dyes or transition metal photocatalysts. Functionalized arylmethane derivatives are obtained in high yield under blue light irradiation with diphenyl phosphate as a catalyst and dihydropyridine derivatives as a radical source.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Jiaying Sun, Wenxuan Zhang, Ran Song, Daoshan Yang, Jian Lv
Summary: Catalytic direct [4 + 2] cycloaddition reactions and Friedel-Crafts reactions of ortho-alkynylnaphthols with benzofurans have been developed. They afford high yields of functionalized hydrobenzofuro[3,2-b]chromans and hydroarylation products, respectively, with high chemoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ferruh Lafzi
Summary: This article presents a metal and additive-free method using acetic acid as a catalyst for the C3-alkylation of indolizines with para-Quinone Methides. The method allows for the synthesis of various substituted indolizine derivatives with good functional group tolerance and high yields (up to 93%). The gram-scale synthesis and product derivatization demonstrate the synthetic potential of this technique.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
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, Physical
Guosong Shen, Faqian He, Wansen Xie, Huanchao Gu, Xiaoyu Yang
Summary: Asymmetric diastereodivergent catalysis is an important strategy for accessing different stereoisomers of a molecule. In this study, a new method for the asymmetric diastereodivergent synthesis of chromanes with C2,C3-contiguous tetrasubstituted stereocenters was reported using chiral phosphoric acid catalysts.
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)
Article
Chemistry, Organic
Alemayehu Gashaw Woldegiorgis, Haorui Gu, Xufeng Lin
Summary: The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were used to synthesize axially chiral styrenes connected to an axially chiral naphthyl-indole unit. By employing chiral phosphoric acid as the catalyst, these axially chiral styrenes were obtained in good yields (up to 96%) and excellent stereoselectivity (up to >99.9% ee, >20:1 dr, and >99:1 E/Z) under mild conditions. Furthermore, further synthetic transformations were achieved with high yields and excellent stereocontrol.
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, Organic
Jing Wang, Tingting Wang, Hongguang Du, Ning Chen, Jiaxi Xu, Zhanhui Yang
Summary: An iridium-catalyzed and phenol-directed deoxygenation method is described for the synthesis of 4-alkylphenols, which offers low catalyst loading, high functionality compatibility, and excellent site-selectivity. The applications in late-stage modification of steroids and gram-scale total synthesis of a Gastrodia elata extract are also highlighted. Mechanistically, the interemediacy of quinone methide controls the site-selectivity, and the formation of iridium hydride serves as the rate-limiting step.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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)
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
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)
Article
Chemistry, Organic
Mei Duan, Jingchao Chen, Ting Wang, Shaojian Luo, Meifen Wang, Baomin Fan
Summary: A wide range of chiral 3-amino-2-oxindoles were successfully synthesized with high optical purities through the enantioselective Friedel-Crafts addition of naphthols with isatin-derived ketimines using H8-BINOL-derived chiral biaryl phosphoric acid as the catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Applied
Yuxue Cao, Guodu Liu
Summary: Chiral phosphoric acid has been a crucial catalyst in chemical synthesis for over five decades. However, a revolutionary approach using photocatalytic excitation of molecules to generate free radicals has emerged in recent years, surpassing the limitations of traditional organic synthesis methods. A significant area of research focuses on chiral phosphoric acid synergistic photocatalysis for enantioselective chemical synthesis, utilizing a bifunctional hydrogen-bonding catalyst.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
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
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
Biochemistry & Molecular Biology
Chang Liu, Jianwei Sun, Pengfei Li
Summary: Due to their unique chemical properties, alpha-alkylidene succinimides are versatile synthons in organic synthesis. However, nucleophilic alkylations of alpha-alkylidene succinimides are limited. In this study, an organocatalytic allylic alkylation of alpha-benzylidene succinimides was established, resulting in the synthesis of optically active succinimides with high yields and enantioselectivities. This strategy also allowed for the construction of pyrrolidine-2,5-dione frameworks with chiral tertiary carbon centers.
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, Multidisciplinary
Yue Tan, Di Huang, Caiming Luo, Jiahao Tang, Ryan T. K. Kwok, Jacky W. Y. Lam, Jianwei Sun, Jinbin Liu, Ben Zhong Tang
Summary: In this study, clearable mercaptosuccinic acid (MSA) coated Au-Ag bimetallic nanoparticles (NPs) were designed to enhance reactive oxygen species (ROS) production. The strong COO-Ag coordination bonds between MSA and Ag atoms on the NPs restricted intrananoparticle motions, leading to enhanced ROS generation. The bimetallic NPs also exhibited pH-responsive self-assembly capability, further boosting ROS production and showing high tumor targeting efficiency and effective cancer cell destruction.
Article
Chemistry, Organic
Zhenkun Yang, Yu Bao, Jiaxin Huang, Zhengyu Han, Jianwei Sun, Hai Huang
Summary: A tandem allylic amination/oxa-Michael addition method utilizing vinylmethylenecyclic carbonates (VMCCs) has been developed to synthesize heterocycles using either single palladium catalysis or palladium-organo relay catalysis. In this process, bisnucleophiles undergo regioselective allylic amination followed by hetero-Michael addition reaction with a second nucleophilic group, resulting in a series of heterocycles. Chiral 3,4-dihydro-2H-benzo[b][1,4]oxazines can be efficiently produced in medium to high yields with good enantioselectivity under palladium-organo relay catalysis.
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
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, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
