Article
Chemistry, Multidisciplinary
F. Wieland Goetzke, Mireia Sidera, Stephen P. Fletcher
Summary: In this study, a novel Rh-catalyzed reaction was reported for the synthesis of chiral, substituted cyclobutanes using asymmetric hydrometallation with salicylaldehydes, enabling subsequent transformations. This has significant implications for the asymmetric synthesis of cyclobutenes.
Article
Chemistry, Multidisciplinary
Binmiao Yang, Jun Dai, Yixin Luo, Kai Kiat Lau, Yu Lan, Zhihui Shao, Yu Zhao
Summary: This method achieves an unprecedented desymmetrization of meso 1,3-diones by enantioselective intermolecular condensation, producing cyclic and acyclic keto-hydrazones with an all-carbon quaternary center in high efficiency and enantioselectivity. The compounds are versatile for preparing multifunctional building blocks and heterocycles with excellent stereoselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Kai-Ge Wen, Chao Liu, Dong-Hui Wei, Yan-Fei Niu, Yi-Yuan Peng, Xing-Ping Zeng
Summary: The chiral phosphoric acid-catalyzed enantioselective condensation of 2,2-disubstituted cyclobutane-1,3-diones with a primary amine provides a mild and efficient method for constructing quaternary carbon-containing cyclobutanes with good to high yields and enantioselectivities. This reaction is the first of its kind, representing a catalytic desymmetrizing carbonyl-amine condensation reaction as well as a catalytic desymmetrizing reaction of prochiral cyclobutane-1,3-dione.
Article
Chemistry, Organic
Takumi K. Suzuki, Masahiro Yamanaka, Takayoshi Arai
Summary: This study reports the asymmetric iodoetherification reaction of unfunctionalized alkenes and its catalyst triZn-II. The reaction shows high enantioselectivity and provides a new platform for the synthesis of chiral morpholines.
Article
Chemistry, Multidisciplinary
F. Wieland Goetzke, Alexander M. L. Hell, Lucy van Dijk, Stephen P. Fletcher
Summary: The study describes an asymmetric cross-coupling reaction between cyclobutenes and arylboronic acids initiated by Rh-catalyzed asymmetric carbometallation. This method allows for the synthesis of highly stereoselective cyclobutane derivatives and demonstrates wide applicability in drug synthesis.
Article
Chemistry, Multidisciplinary
Jian Song, Wen-Hua Zheng
Summary: Despite the widespread use of boronic acids in catalysis, the development of efficient chiral boronic acids remains challenging. In this study, a rational design and a concise synthesis of new C2-symmetric disubstituted boronic acids, or borinic acids, were disclosed. These chiral borinic acids were found to be effective in achieving highly enantioselective desymmetrization of 2,2-disubstituted-1,3-propanediols, leading to chiral diols with a quaternary stereocenter. A range of substrates were successfully utilized in this reaction, providing chiral diols with high enantioselectivity. 11B NMR studies confirmed the presence of tetracoordinate borinate in the catalytic cycle, and a stereocontrol model was proposed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Tian-Yuan Zhao, Ke Li, Liang-Liang Yang, Shou-Fei Zhu, Qi-Lin Zhou
Summary: The highly enantioselective and diastereoselective nickel-catalyzed desymmetrizing cyclization of 1,6-dienes using chiral spiro phosphoramidite ligands provides a new atom- and step-economic approach to chiral spiro lactones and analogues bearing a quaternary stereo-center, which holds significant synthetic application value.
Article
Chemistry, Multidisciplinary
Hanyang Bao, Yunrong Chen, Xiaoyu Yang
Summary: In this study, a highly efficient catalytic asymmetric synthesis of diaryl ether atropisomers was reported via an organocatalyzed enantioselective desymmetrization protocol. The chiral phosphoric acid-catalyzed asymmetric electrophilic aromatic aminations of symmetrical substrates provided a series of diaryl ether atropisomers with excellent yields and enantioselectivities. The utilization of the 1,2-benzenediamine moiety in the products allowed for the facile construction of heterocycles, leading to a wide range of structurally diverse and novel azaarene-containing diaryl ether atropisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Wei Liu, Donglei Wang, Dekun Zhang, Xiaoyu Yang
Summary: Optically active amines are crucial in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. The development of nonenzymatic asymmetric catalytic approaches for the kinetic resolution and desymmetrization of amines in the past two decades has been systematically summarized.
Article
Chemistry, Multidisciplinary
Xianqing Wu, Baixue Luan, Wenyu Zhao, Feng He, Xin-Yan Wu, Jingping Qu, Yifeng Chen
Summary: This study presents a nickel-catalyzed reductive cross-coupling reaction for the desymmetric dicarbofunctionalization of 1,6-dienes. By leveraging an underdeveloped chiral ligand, the reaction selectively forms pyrrolidinones bearing two nonadjacent stereogenic centers, enabling rapid synthesis of complex chiral fused-heterocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Sundaram Maurya, Sandip B. Jadhav, Rambabu Chegondi
Summary: An efficient and mild transition-metal free formal C(sp(2))-H arylation method is reported, which does not require pre-functionalization and is environmentally friendly with high yield.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Yi Li, Wang-Yuren Li, Xiaoxue Tang, Xiaohua Liu, Xiaoming Feng
Summary: The establishment of an asymmetric Heine reaction and the synthesis of a library of pyridine-oxazolines demonstrate the potential of these compounds as chiral ligands and Lewis base catalysts. A possible reaction mechanism was proposed based on control experiments.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Lenin Kumar Verdhi, Asit Ghosh, Natalia Fridman, Alex M. Szpilman
Summary: A copper and chiral nitroxide co-catalyzed aerobic enantioselectiveoxidation process has been developed for the synthesis of axially chiral molecules. Two complementary atroposelective approaches, oxidative kinetic resolution (OKR) and desymmetrization, were studied using ambient air as the terminal oxidant. OKR results in optically pure compounds with er up to 3.5:96.5 and 5.5:94.5 for rac-N-arylpyrrole alcohols and rac-biaryl alcohols, respectively. Desymmetrization of prochiral diols produces axially chiral biaryl compounds with er up to 99:1.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Guang-Jian Mei, Wai Lean Koay, Chun-Yan Guan, Yixin Lu
Summary: Atropisomers beyond the C-C axis have become important additions to the field of axially chiral compounds. Previously considered challenging, these atropisomers characterized by C-N, C-O, C-B, or N-N bonds have been found to possess stable axially chiral frameworks due to their shorter bond lengths and electron-repelling effects. Recent years have seen rapid progress in this emerging area, with various catalytic approaches being reported for their efficient synthesis. These X-Y axially chiral compounds are valuable molecules that can be utilized as ligands or catalysts in asymmetric catalysis or evaluated for their potential biological activities. The chemistry of atropisomers beyond C-C axial chirality is believed to hold an important position in organic chemistry and beyond.
Article
Chemistry, Organic
Qijian Ni, Zhiming Zhu, Yanjun Fan, Xiaoyun Chen, Xiaoxiao Song
Summary: The research has successfully developed an organocatalytic highly diastero- and enantioselective Friedel-Crafts conjugate addition method for adding indolizines to cyclopentenediones to obtain the desired products. The utility of the method was demonstrated through various late-stage functionalizations.
Article
Chemistry, Inorganic & Nuclear
Xin Xu, Zhenyang Lin
Summary: A mild synthetic method for transforming aromatic carbon-oxygen (C-O) bonds into useful molecules was reported. The method involved the use of a carbene complex to catalyze the asymmetric ring-opening reaction of dinaphthofuran with PhMgCl at room temperature. Density functional theory (DFT) calculations were performed to investigate the detailed mechanism, revealing a novel pathway involving Mg(II)-O coordination, phenyl nucleophile migration, and oxidative addition of a C-O bond to Ni(0). Insights into the role of the chiral NHC ligand in inducing enantioselectivity were also obtained.
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
Hou-Lu Liu, Xinyu Wang, Ke Gao, Zhaobin Wang
Summary: In this paper, we report a novel chromium-catalyzed asymmetric cyclopropanation reaction using readily available gem-dihaloalkanes and terminal olefins as precursors. This method provides diverse functionalized chiral cyclopropanes. Mechanistic studies reveal a radical-polar crossover process in this catalytic reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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
Chemistry, Inorganic & Nuclear
Rain Ng, Shun-Cheung Cheng, Ka-Lok Chan, Cheuk-Pui Leung, Wai-Man Cheung, Herman H. -Y. Sung, Hung Kay Lee, Chi-Chiu Ko, Ian D. Williams, Zhenyang Lin, Wa-Hung Leung
Summary: In this study, iridium complexes containing a bis-cyclometalated tripodal CANAC ligand were synthesized and their redox property and reactivity were investigated. Various iridium complexes were successfully obtained through different reactions, and their structures and properties were further studied. The results highlighted the crucial role of the CANAC ligand in stabilizing high-valent iridium.
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, Physical
Wenlong Sun, Chi-Ming Au, Ka-Wa Wong, Ka Lok Chan, Cheuk Kit Ngai, Hung Kay Lee, Zhenyang Lin, Wing-Yiu Yu
Summary: Directarene C-H functionalization by amidyl radicals has made significant progress for arylamides synthesis. Photocatalytic protocols can easily generate amidyl radicals under mild conditions, but designing catalysts with earth-abundant Fe complexes for C-H amidation is an attractive approach for controlling selectivity. However, the preference for high-spin configuration makes it challenging to design robust Fe catalysts for C-H amidation.
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, Physical
Yongheng Jia, Ruichen Li, Yang Zhou, Shenghe Zhao, Hui Yu, Jianpu Wang, Zhenyang Lin, Haibin Su, Ni Zhao
Summary: Perovskite light-emitting diodes (PeLEDs) based on 3D mixed Br-Cl compositions exhibit good color stability and efficiency in the sky-blue range, but suffer from a significant performance decay in the deep-blue emission. This decay is mainly attributed to the poor morphology of the emissive layer. By combining theoretical and experimental approaches, it is discovered that the exchange of halide ions in lead complexes drives the precipitation of CsCl, resulting in low solubility at high Cl/Br ratios and inadequate perovskite film coverage. A metastable dissolution strategy is proposed, leading to deep-blue PeLEDs with a record high EQE of 4% and excellent spectral stability.
Article
Chemistry, Multidisciplinary
Zhongming Cheng, Tilong Yang, Can Li, Yunshun Deng, Fangjia Zhang, Pinhong Chen, Zhenyang Lin, Shengming Ma, Guosheng Liu
Summary: This study presents a copper-catalyzed radical relay strategy for the site-selective cyanation of sp(2) C-H bonds in allenes. The reactions show broad substrate scope and remarkable functional group compatibility under mild conditions. The site-selectivity is attributed to the unique pocket created by the Cu-bound nitrogen-centered radical and the crucial hydrogen bonding between the fluoride and the hydrogen atom. Late-stage functionalization of drug-like bioactive molecules containing an allene motif becomes feasible.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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)
