Review
Chemistry, Physical
Changgong Xu, Carlyn Reep, Jamielyn Jarvis, Brandon Naumann, Burjor Captain, Norito Takenaka
Summary: This review discusses the application and challenges of catalytic enantioselective ketimine Mannich and related reactions in synthesizing chiral building blocks. Various approaches have been developed to overcome the adverse properties of ketimines in these transformations.
Article
Chemistry, Organic
Fei Li, Zhuo Li, Youming Wang, Zhenghong Zhou
Summary: A mild and efficient organocatalyzed [3+2] cycloaddition reaction between isatin-derived ketimines and 2-ylideneindane-1,3-diones has been achieved. The resulting spiro[oxindole-3,2'-pyrrolidine] compounds, containing both spiro indane-1,3-dione motif and a trifluoromethyl group, were obtained in high yields with good diastereo- and enantioselectivities.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Qianwen Gao, Chenggui Wu, Shuang Deng, Lisha Li, Ze-Shui Liu, Yu Hua, Jinxiang Ye, Chang Liu, Hong-Gang Cheng, Hengjiang Cong, Yinchun Jiao, Qianghui Zhou
Summary: A modular and convergent strategy for assembling atropisomeric o-terphenyls with 1,2-diaxes via palladium/chiral norbornene cooperative catalysis and axial-to-axial diastereoinduction is reported. The method utilizes readily available aryl iodides, 2,6-substituted aryl bromides, and potassium aryl trifluoroborates as building blocks, allowing for diversity-oriented synthesis and step economy. DFT calculations rationalize the axial-to-axial diastereoinduction process, demonstrating the synthetic utilities of this approach.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Kenta Arai, Yuumi Sato, Ikumi Nakajima, Manami Saito, Moeka Sasaki, Akiko Kanamori, Michio Iwaoka
Summary: Amphiphilic derivatives of (+/-)-trans-1,2-diselenane-4,5-diol were employed as GPx-like catalysts for the reduction of H2O2 and lipid peroxidation. The compounds with hydrophilic groups showed high antioxidative activities for H2O2 reduction, while lipophilic compounds with long alkyl chains or aromatic substituents were more effective against lipid peroxidation. These compounds exhibited low cytotoxicity and promising anti-lipid peroxidative activities, indicating their potential as selenium-based antioxidative drugs.
BIOORGANIC & MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Ying Zou, Zhi-Cheng Huang, Min Xiang, Chen-Yi Li, Xia Li, Fang Tian, Li-Xin Wang
Summary: A spiro scaffold chiral organocatalyst was prepared from racemic spiro-oxindole amine using L-menthol in 4 steps with 28%-40% overall yields, showing superior catalytic activity and selectivity in enantioselective aldol condensation. High yields and ee values up to 96% were achieved for most substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Automation & Control Systems
Varvara S. Alabusheva, Vladimir V. Shilovskikh, Liubov A. Bridenko, Vladislav V. Gurzhiy, Ekaterina V. Skorb
Summary: This study proposes a direct synthesis approach for creating anisotropic microswimmers as an alternative to top-down fabrication methods for asymmetric artificial swimmers. Melamine barbiturate (MBA) self-assembled supramolecular crystals are used as an asymmetric matrix for selective chemical platinum deposition. The surface functional groups of the crystals provide acidic sites for platinum sorption, leading to the formation of a platinum catalytic layer. The MBA asymmetric swimmers show directional motion in a fuel environment, and previous studies have shown that MBA has pH-dependency and encapsulation capacity, offering opportunities for the formation of functional materials.
ADVANCED INTELLIGENT SYSTEMS
(2023)
Article
Chemistry, Inorganic & Nuclear
Shota Hagiwara, Atsuya Momotake, Takashi Ogura, Sachiko Yanagisawa, Akihiro Suzuki, Saburo Neya, Yasuhiko Yamamoto
Summary: The catalytic cycle of a peroxidase-mimicking heme-DNAzyme involves an intermediate known as compound I, formed through O-O bond cleavage of an Fe3+-bound hydroperoxo ligand. Peroxidase assaying was performed to elucidate the effects of heme electronic structure and local heme environment on catalytic activity. The study revealed that the activity of the heme-DNAzyme can be controlled independently through heme electronic structure and local environment, enhancing the understanding of the structure-function relationship.
INORGANIC CHEMISTRY
(2021)
Article
Environmental Sciences
Yulong Liu, Xianxian Sheng, Zhikang Zhou, Peng Wang, Zhanpeng Lu, Jiaqi Dong, Shuguang Lyu
Summary: In this study, nano-calcium peroxide (nCP) was successfully synthesized and showed superior performance in naphthalene (NAP) removal compared to commercial calcium peroxide (CP) when catalyzed by Fe(II). The addition of citric acid (CA) was found to significantly enhance NAP removal efficiency in the nCP/Fe(II)/CA system, with HO• identified as the dominant radical for NAP degradation. Overall, the nCP/Fe(II)/CA system exhibited great potential for the remediation of NAP-contaminated groundwater, achieving 97.7% removal of NAP in actual groundwater samples.
WATER AIR AND SOIL POLLUTION
(2021)
Article
Chemistry, Multidisciplinary
Fei Tian, Wu-Lin Yang, Tao Ni, Jian Zhang, Wei-Ping Deng
Summary: The development of efficient methods for synthesizing chiral polycyclic indoles is crucial for their wide applications in medicines, pesticides, and other functional molecules. The study revealed novel indolyl substituted metal-allyl zwitterionic intermediates that could participate in asymmetric cycloaddition reactions with high selectivities, leading to the synthesis of diverse chiral polycyclic indoles.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Mikhail A. Emelyanov, Nadezhda Stoletova, Alexander F. Smol'yakov, Mikhail M. Il'in, Victor Maleev, Vladimir A. Larionov
Summary: The study presents the synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (R,R)-1,2-diphenylethylenediamine and salicylaldehyde. These complexes exhibited high selectivity and catalytic activity in challenging kinetic resolution reactions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Monojit Batabyal, Aditya Upadhyay, Rahul Kadu, Nihal Chaitanya Birudukota, Deepak Chopra, Sangit Kumar
Summary: Research has found that organoselenium compounds with chalcogen-bonding interactions can play a significant role as catalysts in oxidation reactions, and can efficiently catalyze the disproportionation of hydrogen peroxide and bromination of arenes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Arash Ghorbani-Choghamarani, Zahra Taherinia
Summary: This article discusses the application of greener methods in the synthesis of sulfoxides and the study on sulfinylation reaction methods. Various compounds have been synthesized through different pathways, providing new insights into the preparation of sulfoxides.
Article
Chemistry, Multidisciplinary
Guannan Wang, Hai Huang, Wengang Guo, Chenxiao Qian, Jianwei Sun
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Wengang Guo, Yuzheng Luo, Herman H-Y Sung, Ian D. Williams, Pingfan Li, Jianwei Sun
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Tianyu Zhang, Han Zhuang, Luning Tang, Zhengyu Han, Wengang Guo, Hai Huang, Jianwei Sun
Summary: A novel intramolecular C-C formation process based on catalytic asymmetric oxetane opening by carbon nucleophiles has been developed, allowing for the rapid synthesis of valuable enantioenriched 2,3-dihydrobenzo[b]oxepines under mild conditions with good chemical efficiency and enantioselectivity. The products also serve as useful precursors to other valuable structures.
Article
Chemistry, Organic
Luning Tang, Yu Zang, Wengang Guo, Zhengyu Han, Hai Huang, Jianwei Sun
Summary: B(C6F5)3 catalyzes the unusual doublereduction of oxetanes by hydrosilane with aryl migration via neighboring group participation. Control experiments suggest that the phenonium ion serves as the key intermediate. Minor modifications of this protocol also enable simple hydrosilylative opening of oxetanes.
Letter
Chemistry, Organic
Zhengyu Han, Han Zhuang, Luning Tang, Yu Zang, Wengang Guo, Hai Huang, Jianwei Sun
Summary: A catalytic asymmetric allylic substitution/isomerization process with central chirality transposition has been developed. This process utilizes the ambident reactivity of the 2-indole imine methide generated in situ from racemic tertiary indolylmethanols, allowing regioselective formation of a C-C bond at the 3 position and enantiocontrolled construction of a stereogenic center at the 2-benzylic position.
Article
Chemistry, Multidisciplinary
Ying Zhou, Xin Yue, Feng Jiang, Jianwei Sun, Wengang Guo
Summary: This article reports an efficient organocatalytic formal N-H insertion reaction of arylamines with alpha-keto sulfoxonium ylides bearing two aryl groups, resulting in a broad range of alpha-tertiary aminoketones with good to excellent yields and enantioselectivities (up to 90% yield and 94% ee). The usefulness of this methodology is further demonstrated by the facile synthesis of enantioenriched 2-amino-1,2-diarylethanol bearing two different aryl groups, which represents an important building block with limited access.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wengang Guo, Ying Zhou, Hongling Xie, Xin Yue, Feng Jiang, Hai Huang, Zhengyu Han, Jianwei Sun
Summary: In this study, the first metal-free asymmetric H-X bond insertion of its kind was achieved by utilizing visible light as a promoter and a chiral phosphoric acid as a catalyst. Under mild conditions, alpha-diazoesters and aryl amines smoothly underwent N-H bond insertion to form enantioenriched alpha-aminoesters with high efficiency and good enantioselectivity. The key to success was the use of DMSO as an additive, which facilitated the rapid capture of the highly reactive free carbene intermediate to form a domesticated sulfoxonium ylide.
Article
Chemistry, Organic
Ying Zhou, Yan Zhang, Canghai Yu, Xin Yue, Feng Jiang, Wengang Guo
Summary: This study discovered a method that utilizes high energy intermediates to construct valuable chiral products. By catalytic asymmetric protonation of in situ generated ammonium ylide using chiral Bronsted acid under visible-light irradiation, the desired α-amino esters were obtained with moderate to high enantioselectivity and yield. This method not only demonstrates the compatibility of chiral phosphoric acid catalysis with free carbene insertion reactions, but also indicates the significance of arylamine's pKa value in tuning the enantioselectivity of the reaction.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Feng Jiang, Tengfei Meng, Ying Zhou, Zhenying Xiong, Yupei Zhao, Wengang Guo
Summary: We report an enantio- and diastereodivergent synthesis of enantioenriched fluorenes with broad substrate scope and high enantioselectivity (up to 99% ee) under low catalyst loading (0.1 mol %). The success of this method lies in the pseudo-diastereodivergent desymmetrization of stereoisomers of meso-epoxides enabled by the same organocatalyst. Furthermore, some of the chiral fluorenes obtained exhibit high fluorescence quantum yields (up to 76.6%), as evidenced by photophysical properties studies.
Article
Chemistry, Multidisciplinary
Xin Yue, Ying Zhou, Yan Zhang, Tengfei Meng, Yupei Zhao, Wengang Guo
Summary: In this study, we have developed a sequential visible-light-promoted Wolff rearrangement of 1-diazonaphthalen-2(1H)-ones, followed by capturing the in situ generated ketene intermediates with various alcohols, resulting in diverse 1H-indene-3-carboxylates in moderate to good yields under mild reaction conditions. The broad substrate scope, high functional group tolerance, and robust conditions make the resulting derivative a versatile platform for the synthesis of numerous bioactive molecules.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhibing Weng, Ying Zhou, Xin Yue, Feng Jiang, Wengang Guo
Summary: In this study, catalytic asymmetric alpha-regioselective Michael additions of vinylogous alpha-ketoester enolates were conducted efficiently using a chiral bifunctional organocatalyst. The reactions yielded Rauhut-Currier type products with high yields and excellent regio- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Wengang Guo, Feng Jiang, Shijia Li, Jianwei Sun
Summary: A catalytic asymmetric azidation reaction for the efficient synthesis of alpha-azido ketones bearing a labile tertiary stereocenter is disclosed. Detailed mechanistic studies provided important insights into the reaction pathway, and a simplified alternative protocol using a cheaper HN3 source was developed.
Article
Chemistry, Multidisciplinary
Zhengyu Han, Yu Zang, Chang Liu, Wengang Guo, Hai Huang, Jianwei Sun
Summary: A new organocatalytic asymmetric method for the synthesis of enantioenriched triarylmethanes has been developed, which employs asymmetric reduction via C-H bond formation as the key step, without requiring the presence of a heteroaryl ring or the presynthesis of unstable para-quinone methides.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Wengang Guo, Min Wang, Zhengyu Han, Hai Huang, Jianwei Sun
Summary: The research describes the first organocatalytic asymmetric N-H insertion reaction using alpha-carbonyl sulfoxonium ylides, providing efficient access to alpha-aryl glycines with excellent enantiocontrol. The high stability and weak basicity of sulfoxonium ylides make this protocol user-friendly and practically useful, with detailed mechanistic studies revealing reversible protonation and rate-determining C-N bond formation.
Article
Chemistry, Multidisciplinary
Ping Chen, Kai Wang, Boyu Zhang, Wengang Guo, Yan Liu, Can Li
CHEMICAL COMMUNICATIONS
(2019)
