Article
Chemistry, Multidisciplinary
Mario Waser, Michael Winter, Christopher Mairhofer
Summary: This article introduces the significance of (thio)-urea-containing bifunctional quaternary ammonium salts as organocatalysts and their application in asymmetric method development. It provides an overview of catalyst design and highlights the author's own contributions.
Article
Chemistry, Organic
Changming Xu, Yinsheng Qi, Xinshuang Yang, Xiangfan Li, Zhenpeng Li, Lei Bai
Summary: A class of C2-symmetric chiral spirocyclic phase-transfer catalysts based on the tetramethyl-1,1'-spirobiindane scaffold was synthesized in 12 steps from commercially available bisphenol A with total yields between 22-25%, featuring a more rigid and stable backbone and smaller dihedral angles that can be easily modified. These catalysts exhibit high catalytic performance in the asymmetric alkylation of tert-butyl glycinate Schiff base at only 2 mol % loading, resulting in target products with yields of up to 92% and 98% ee.
Review
Chemistry, Multidisciplinary
Shovan Mondal, Frederic Dumur, Didier Gigmes, Mukund P. Sibi, Michele P. Bertrand, Malek Nechab
Summary: Benefiting from the increase in fundamental knowledge, there has been a continuous burst of new ideas and catalytic methods for enantioselective radical reactions in the past 20 years. This review provides a comprehensive survey of the progress achieved during this period, focusing on chiral organocatalysts and transition-metal redox catalysis. The review also discusses the merger of photocatalysis with organo- or metalla-photocatalysis and enzyme-catalyzed reactions involving radical intermediates.
Article
Chemistry, Organic
Liang-Liang Yang, Jin Cao, Tian-Yuan Zhao, Shou-Fei Zhu, Qi-Lin Zhou
Summary: The highly enantioselective Si-H bond insertion reaction of alpha-aryldiazoacetates catalyzed by chiral spiro dirhodium tetraphosphate was successfully developed, leading to the preparation of various chiral alpha-silyl esters with high yield and excellent enantioselectivity. Even challenging substrates for other chiral dirhodium catalysts showed good results in this reaction, making it one of the few successful applications of chiral dirhodium phosphates in asymmetric catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Mustafa Zahrittin Kazancioglu
Summary: Two different amino piperazine derivatives with various halogen groups were synthesized and further transformed to yield eight different sulfonamides and urea derivatives. The aryl bromide functionality in the parent amino piperazines was utilized in the Suzuki coupling reaction to obtain potentially bioactive piperazine derivatives.
POLYCYCLIC AROMATIC COMPOUNDS
(2022)
Review
Chemistry, Multidisciplinary
Chen-Xi Ye, Eric Meggers
Summary: Asymmetric transition metal catalysis is an important tool for synthesizing chiral molecules in an enantioselective manner. This article discusses the design and development of a new class of C2-symmetric chiral-at-ruthenium catalysts, which can exhibit high catalytic activity and excellent stereocontrol in asymmetric nitrene C-H insertion reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Review
Chemistry, Applied
Hao-Qiang Cao, Jun-Kuan Li, Fa-Guang Zhang, Dominique Cahard, Jun-An Ma
Summary: This review comprehensively summarizes modern synthetic methods towards asymmetric construction of chiral amino carboxylic-phosphonic acid derivatives, including phosphono-containing amino acid derivatives and catalytic enantioselective synthesis as a potent strategy. Topics such as chiral resolution protocols, chiral auxiliary-directed syntheses, and valorization of abundant chiral amino acid resources are also discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Chunhui Zhang, Jijun Jiang, Xiaoyu Huang, Jun Wang
Summary: A new type of CpRh(III) catalyst has been successfully designed and synthesized for asymmetric C-H activation. The catalyst, with prochiral tetrasubstituted Cp-px ligands, showed high catalytic activity in various reactions, achieving high yields and enantiomeric excesses.
Article
Chemistry, Physical
Takuya Murai, Wenjie Lu, Toshifumi Kuribayashi, Kazuhiro Morisaki, Yoshihiro Ueda, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Norihiro Tokitoh, Takeo Kawabata, Takumi Furuta
Summary: D-2-symmetric dirhodium(II) carboxylate catalysts bearing axially chiral binaphthothiophene delta-amino acid derivatives have been developed, with conformational control supported through chalcogen-bonding interactions providing well-defined and uniform asymmetric environments. These complexes act as asymmetric catalysts for stereoselective intramolecular C-H insertion to yield various cis-alpha,beta-diaryl gamma-lactones, with high diastereo- and enantioselectivities, and can also be used for short total syntheses of naturally occurring gamma-lactones.
Article
Chemistry, Multidisciplinary
Kristine Klimovica, Julius X. Heidlas, Irvin Romero, Thanh V. Le, Olafs Daugulis
Summary: This article reports sandwich diimine-copper(I) catalysts for C(sp(3))-H bond functionalization, demonstrating rare examples of base-metal catalyzed, intermolecular C(sp(3))-H functionalizations using unactivated diazo compounds. The electrophilicity and unique steric environment of the sandwich-copper catalysts are likely reasons for their catalytic efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Fereshteh Ahmadi, Kaveh Imani, Hadi Mozafari, Ayoob Bazgir
Summary: An efficient iodine-catalyzed reaction for the synthesis of benzothiazolyl urea derivatives via a metal-free isocyanide insertion reaction is reported in this study. The strategy offers the advantages of a simple synthesis method and the use of more affordable iodine catalyst instead of expensive transition metal catalysts.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Jason R. Combs, Yin-Chu Lai, David L. Van Vranken
Summary: Allyl 2-diazo-2-phenylacetates react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate alpha-allyl-a-thio silyl esters. The reaction involves a tandem process of carbene group insertion into the S-Si bond and Ireland-Claisen rearrangement. The products are isolated as carboxylic acids after aqueous workup, with intramolecular cyclopropanation and heteroatom addition competing during the reaction.
Review
Chemistry, Multidisciplinary
Oleksandr Vyhivskyi, Anton Kudashev, Takeru Miyakoshi, Olivier Baudoin
Summary: Processes involving transition-metal catalysis have become a major part of synthetic chemists' toolbox in recent decades. The focus has shifted from cross-coupling reactions to C-H bond functionalization, with constant progress leading to discovery of enantioselective methods. The review discusses enantioselective Pd-0-catalyzed C-H activation, highlighting the importance of different chiral ligands and catalysts in enabling these transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Pierre Milbeo, Jean Martinez, Muriel Amblard, Monique Calmes, Baptiste Legrand
Summary: The improvement of molecular diversity is a major focus of chemists, who aim to develop versatile platforms with highly controlled chemical three-dimensional space. Cyclic beta-amino acids are of great interest in various fields of chemistry. By incorporating these acids into oligomers, original structures have been successfully stabilized with recent successes in health, material science, and catalysis.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Hui-Na Zou, Yu-Tao Zhao, Liang-Liang Yang, Ming-Yao Huang, Jing-Wei Zhang, Meng-Lin Huang, Shou-Fei Zhu
Summary: Chiral propargylic boron compounds have a wide range of potential applications, but the synthesis of these compounds with high enantioselectivity is still unknown. This study reports a catalytic method for the construction of chiral propargylic boron compounds with high enantioselectivity.
Article
Chemistry, Multidisciplinary
Dan Ni, Longlong Song, Yun Zhao, Shunying Liu
Summary: A Rh(II)/boron reagent co-catalyzed transformation was developed for the efficient synthesis of multi-substituted conjugated dienones under mild conditions. By trapping allene carbocations with oxonium ylides, two C=C double bonds, one C-C single bond, and one C-O single bond were constructed in yields up to 85%. Furthermore, a diversity-oriented strategy was established for the synthesis of alkyne ether and dihydrofuran derivatives in a substrate-dependent manner.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Medicinal
Yaqi Deng, Rou Pi, Li Niu, Yun Zhao, Dan Ni, Longlong Song, Zi Li, Wangyujing Han, Qinghua Wei, Yuqiao Han, Tong Zhu, Zhengli Luo, Donghui Sun, Suzhen Dong, Shunying Liu
Summary: This study identified a potential drug candidate for the treatment of osteosarcoma, which demonstrated significant cellular potency and in vivo efficacy by modulating the solubility of compounds. The candidate compound also showed inhibition of OS cell migration.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Ji, Cong Guan, Qinghua Wei, Xuwen Chen, Yun Zhao, Shunying Liu
Summary: This study developed a highly regioselective synthesis of N-2-substituted 1,2,3-triazoles using N-sulfonyl-1,2,3-triazoles and alkyl bromides/alkyl iodides at room temperature. The mechanistic pathway proposed explains the high N-2 regioselectivity, and the protocol showed good to excellent product yields (72-90%).
Article
Chemistry, Organic
Xiangrong Liu, Xue Tian, Jiawu Huang, Yu Qian, Xinfang Xu, Zhenghui Kang, Wenhao Hu
Summary: An enantioselective three-component reaction of alpha-propargylic-3-indolymethanol with diazoindolinone and alcohol has been achieved under the cocatalysis of Rh(II) and chiral phosphoric acid (CPA). The reaction proceeds through regio- and enantiospecific addition of an in situ formed oxonium ylide to the alpha-propargylic indole iminium ion, providing an efficient access to chiral propargylic indole derivatives with high yields and enantioselectivities.
Article
Chemistry, Organic
Cong Guan, Jian Ji, Zi Li, Qinghua Wei, Xiang Wu, Shunying Liu
Summary: An efficient one-pot two-step synthetic strategy has been developed for the highly selective synthesis of N-2-substituted-1,2,3-triazole via a radical transformation from aryl ethynylenes, azides, and furan. A total of 17 examples of aryl ethynylene with different substituents were successfully converted into their corresponding functionalized N-2-substituted-1,2,3-triazole derivatives with good yields.
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Chemistry, Organic
Xiang Fu, Jie Tang, Ruyu Hua, Xiaoqian Li, Zhenghui Kang, Huang Qiu, Wenhao Hu
Summary: This study reports two DNA-compatible reactions with alkenes and diazo compounds, providing hydroalkylation and cyclopropanation products in moderate to excellent yields. These transformations not only offer new access to C(sp3)-C(sp3) bond formation in DELs with excellent functional group tolerance, but also represent practical ligation methods to introduce functionalized molecules into DNA.
Article
Oncology
Shuncong Wang, Lei Chen, Yuanbo Feng, Johan Swinnen, Charles Jonscher, Chantal Van Ongeval, Yicheng Ni
Summary: This study examines the prevalence and prognosis of synchronous lung metastasis (sLM) among cancer patients based on the SEER database. The findings reveal disparities in sLM by primary cancer type and clinicodemographic factors, highlighting the need for risk assessment and prognosis classification tools in clinical management.
Letter
Chemistry, Organic
Jian Xue, Zhengli Luo, Jisheng Huang, Yaqi Deng, Suzhen Dong, Shunying Liu
Summary: An asymmetric catalytic approach for the construction of C3-multifunctionalization alpha-hydroxy-beta-amino pyridines has been developed. The method utilizes two chiral catalysts to modulate the reaction independently, leading to high yield and good enantioselectivity. The resulting products exhibit selective antiosteosarcoma activity on 143B cells.
Article
Chemistry, Physical
Longlong Song, Lulu Xiong, Dan Ni, Weixiong Chen, Jian Ji, Jian Xue, Xuwen Chen, Xiang Wu, Xiao He, Shunying Liu
Summary: Here, we report a [Pd-(eta(3)-C3H5)-Cl](2)/Sc-(OTf)(3)-catalyzed catalytic process accelerated by Bronsted acids with a beta-selective aza-Michael addition to yield a gamma-quaternary carbon. The triple co-catalytic system provides a strategy for the activation of vinyl-quinolines with a linear selectivity containing gamma-quaternary carbon, and the developed method shows a broad substrate scope, providing a general and rapid strategy for the quinoline-based diverse library construction.
Article
Chemistry, Organic
Cong Guan, Jiabin Yin, Jian Ji, Jinhua Liu, Xiang Wu, Tong Zhu, Shunying Liu
Summary: A regioselective electrochemical C-H amination method using easily accessible ethers has been developed to synthesize N (2)-substituted 1,2,3-triazole. Multiple substituents, including heterocycles, were well-tolerated, and 24 examples were obtained in moderate to good yields. Control experiments and DFT calculations revealed that the electrochemical synthesis occurs through a N-tosyl 1,2,3-triazole radical cation process, promoted by single-electron transfer from the lone pair electrons of the aromatic N-heterocycle, and the desulfonation is responsible for the high N (2)-regioselectivity.
Article
Chemistry, Multidisciplinary
Jian Ji, Zongjing Hu, Cong Guan, Jinhua Liu, Yaqi Deng, Xuwen Chen, Shunying Liu
Summary: An efficient method for the 1,2-carbotriazolization of alkenes with N-sulfonyl-1,2,3-triazoles and aldehydes has been developed using a copper-catalyzed radical relay process. This strategy enables the production of beta-triazolized ketones with high regio- and chemoselectivity, and has a wide substrate scope. The resulting beta-triazolized ketone scaffold shows promising inhibitory activity on osteosarcoma cell lines, making it a potential pharmacophore for drug discovery.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Longlong Song, Lulu Xiong, Dan Ni, Weixiong Chen, Jian Ji, Jian Xue, Xuwen Chen, Xiang Wu, Xiao He, Shunying Liu
Summary: This study reports a [Pd(eta 3-C3H5)Cl]2/Sc(OTf)3 catalytic system accelerated by Brønsted acids for the selective aza-Michael addition of vinyl-substituted quinolines, diazos, and anilines/alcohols. The activation of the corresponding Lewis acid by the generation of anhydride analogues from Brønsted acid and the counter anion (OTf-) promotes nearly quantitative transformation. The triple co-catalytic system provides a strategy for the activation of vinylquinolines with a linear selectivity containing gamma-quaternary carbon.
Article
Chemistry, Organic
Ji Jian, Liu Jinhua, Guan Cong, Chen Xuwen, Zhao Yun, Liu Shunying
Summary: The green and efficient synthesis of N-2-substituted 1,2,3-triazoles was achieved by coupling cheap and easily available alcohols with N-sulfonyl-1,2,3-triazole using in-situ generated sulfonic acid as a catalyst. The reaction exhibited high regioselectivity and good yields without the need for additional catalysts or additives. Mechanistic studies suggested that the reaction was promoted by methanesulfonic acid (MsOH) generated from the hydrolysis of N-sulfonyl-1,2,3-triazoles, and high regioselectivity was achieved through a thermally stable intermediate.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhengli Luo, Xuwen Chen, Jian Xue, Yaqi Deng, Suzhen Dong, Shunying Liu
Summary: A method has been developed for the rapid and efficient synthesis of benzosultams containing continuous quaternary carbons in a one-pot fashion, with moderate to excellent yields at room temperature. The resulting products exhibit good anticancer activity in osteosarcoma cells.
ORGANIC CHEMISTRY FRONTIERS
(2022)
