Article
Chemistry, Multidisciplinary
Chenxiao Qian, Pengfei Li, Jianwei Sun
Summary: A catalytic enantioselective variant of oxidative rearrangement of indoles to access oxindoles has been developed using chiral phosphoric acid catalysis, providing a rapid access to a range of enantioenriched spirooxindoles with high enantioselectivity controlled by dynamic kinetic resolution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Vasco Corti, Mathias Kirk Thaegersen, Valdemar Juel Enemaerke, Nomaan M. Rezayee, Casper L. Barlose, Karl Anker Jorgensen
Summary: The first atroposelective aminocatalytic methodology for the construction of C-N atropisomers is described. By directly coupling indole-2-carboxaldehydes to ortho-quinones, a new library of functionalized and enantioenriched C-N atropisomers was obtained using a designed and synthesized aminocatalyst. The synthetic utility of these atropisomers was demonstrated through various transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Tao Wang, Bo Huang, You-Qing Wang
Summary: Using chiral phosphoric acids as organocatalysts, a formal asymmetric (4+2) cycloaddition of 3-methylene isoindolinone and in situ-generated ortho-quinone methide substrates is achieved. This reaction allows the construction of spiro chroman-isoindolinones containing spiro-N,O-heterocycles with high enantioselectivity, with a broad substrate scope.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Avene C. Colgan, Rupert S. J. Proctor, David C. Gibson, Padon Chuentragool, Antti S. K. Lahdenpera, Kristaps Ermanis, Robert J. Phipps
Summary: This study reports a significant advancement in the catalytic enantioselective Minisci reaction, allowing the use of α-hydroxy radical coupling partners to obtain valuable enantioenriched secondary alcohol products. The approach is highly regioselective as well as highly enantioselective.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Vojtech Docekal, Tereza Koberova, Jan Hrabovsky, Andrea Vopalenska, Robert Gyepes, Ivana Cisarova, Ramon Rios, Jan Vesely
Summary: A new asymmetric organocatalytic cascade reaction was reported for the synthesis of enantiopure chiral boron dipyrromethenes (BODIPYs), with high isolated yields and enantiomeric excesses. The method showed synthetic versatility and was successfully applied to a series of additional transformations of the corresponding optically pure compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Suman K. Saha, Anupriya Bera, Soniya Singh, Nirmal K. Rana
Summary: Nitrogen-containing heterocyclic compounds have been extensively studied for their significant applications in synthetic organic chemistry, agrochemicals, and pharmaceuticals. alpha,beta-Unsaturated imines or conjugated imines have been found to react with a versatile family of compounds, leading to the synthesis of important cyclic and acyclic products. This review highlights the recent advances in enantioselective reactions of alpha,beta-unsaturated imines and their synthetic methodologies for synthesizing nitrogen-containing heterocycles containing four to six-membered rings. Additionally, the synthesis of rarely found seven, eight, and nine-membered nitrogen-containing heterocycles is also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ryuichi Nishiyori, Megumi Okada, John R. J. Maynard, Seiji Shirakawa
Summary: This study demonstrated the successful development of highly enantioselective bromolactonizations of 4-aryl-4-pentenoic acids using BINOL-derived chiral bifunctional sulfide catalysts, highlighting the importance of the bifunctional design in chiral sulfide catalysts. The catalytic asymmetric reaction system could also be applied to highly stereoselective desymmetrizing bromolactonizations, showing promising potential for further applications in asymmetric synthesis.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Caroline Dorsch, Christoph Schneider
Summary: We describe a catalytic asymmetric cyclization of 1-aryl terpenols to produce enantiomerically enriched Delta(9)-cis-tetrahydrocannabinoid scaffolds in a one-step process. Powerful chiral catalysts, strongly acidic imidodiphosphorimidates (IDPis), were identified to give the products in good yields and excellent enantioselectivity. After MOM-deprotection, some naturally occurring cannabimimetics such as (-)-cis-Delta(9)-tetrahydrocannabinol and (-)-perrottetinene, as well as some unnatural analogues, were accessible through a simple 3-step biomimetic sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Editorial Material
Chemistry, Physical
Svetlana B. Tsogoeva, Guangbin Dong, Lutz Ackermann
Summary: This Special Collection discusses the latest strategies and progress in ring synthesis, including catalytic domino reactions and one-pot processes. Contributions cover transition-metal catalysis, organocatalysis, nanocatalysis, and photoredox catalysis for preparing carbocyclic and heterocyclic compounds.
Article
Chemistry, Organic
Xuebo Gao, Rong Chang, Junxin Rao, Danyang Hao, Zhuxia Zhang, Cong-Ying Zhou, Zhen Guo
Summary: Here, we report a halogen-bonding-based electron donor-acceptor (EDA) complex-promoted photoreaction for the synthesis of C2-malonylated indoles. The protocol allows for the efficient coupling of indoles with diethyl bromomalonate under visible-light irradiation without the need for any transition-metal catalyst or photocatalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiao-Wen Zhang, Ming-Hui Zhu, Hai-Xiang Zeng, Qi-Yang Li, Wen-Bo Liu
Summary: This study presents a highly enantioselective NiH-catalyzed hydrocyclization of alkynones, yielding an array of enantioenriched heterocyclic tertiary allylic alcohols. The choice of precatalysts significantly influences the selectivity of the products, with yields reaching up to 81%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Nobuya Tsuji, Pavel Sidorov, Chendan Zhu, Yuuya Nagata, Timur Gimadiev, Alexandre Varnek, Benjamin List
Summary: Catalyst optimization processes often rely on qualitative assumptions of chemists based on screening data, while machine learning models using molecular properties or calculated 3D structures are time-consuming and costly. This study proposes a machine learning model based on fragment descriptors, which are fine-tuned for asymmetric catalysis and result in robust and efficient virtual screening. Through theoretical design and experimental validation, new catalysts with higher selectivities in a challenging synthesis were developed using only moderately selective training data.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chiara Volpe, Sara Meninno, Carlo Crescenzi, Michele Mancinelli, Andrea Mazzanti, Alessandra Lattanzi
Summary: This study demonstrates an enantioselective one-pot catalytic strategy for the synthesis of dihydroquinoxalinones, using a combination of catalysts and intermediates to achieve high enantioselectivity in the formation of medicinally relevant heterocycles. The reusability of the organocatalyst and the mechanistic insights into the DROC process provide valuable information for further development of enantioselective synthesis strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Antonia Di Mola, Felice De Piano, Lorenzo Serusi, Giovanni Pierri, Laura Palombi, Antonio Massa
Summary: The investigation of the reactivity of an alpha-amido sulfone derived from 2-formyl benzoate under organocatalytic conditions in the presence of acetylacetone allowed the synthesis of a new heterocyclic hybrid isoindolinone-pyrazole with high enantiomeric excess. Dibenzylamine was also used as a nucleophile to afford an isoindolinone with aminal substituent in 3-position in suitable selectivity. The use of Takemoto's bifunctional organocatalyst not only led to observed enantioselectivity but was also important in accomplishing the cyclization step in both cases. Notably, this catalytic system proved to be particularly effective in comparison to widely used phase transfer catalysts.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(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
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
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
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)
