Article
Chemistry, Organic
Dwaipayan Das, Agniva Das, Saiful Islam, Asish R. R. Das, Adrita Banerjee, Romit Majumder, Debasish Bandyopadhyay
Summary: An efficient and intriguing method using Rh(II) catalysis has been developed for the preparation of fused furan moieties. The technique involves a one-pot C-H activation/concomitant tandem annulation process using an enolic compound and a beta-keto sulfoxonium ylide as reactants. The synthesis only requires Rh-2(TFA)(4) as the catalyst, removing the need for additional metallic or nonmetallic additives. This transformation of naphthoquinone fused furan into highly decorated naphthoquinone fused indolizines shows great promise in synthetic applications.
Article
Chemistry, Organic
Kosuke Nakashima, Sumire Hanamura, Aoi Imamura, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: This study investigates the asymmetric Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated trifluoromethyl ketones using a squaramide organocatalyst. The squaramide organocatalyst efficiently promotes the reaction, yielding products with both indole motif and trifluoromethyl group in high yields and excellent enantioselectivities (up to 99% ee). The transformation of the obtained adduct to a chiral spiro indoline 3-one is also demonstrated.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Duc Chu, Jonathan A. Ellman
Summary: Straightforward and mild metal-free three-component Friedel-Crafts approaches using hexafluoroisopropanol (HFIP) as mediator were reported for the synthesis of alkenyl and alkyltrifluoromethyl sulfides from arenes, (PhSO2)2NSCF3, and alkynes or alkenes. The transformations showed high regio- and stereochemical control through the formation of cationic thiirenium and thiiranium intermediates followed by Friedel-Crafts reactions with arenes. A mechanistically related three-component synthesis of alkenyl iodides from arenes, alkenes, and N-iodosuccinimide was also described.
Article
Chemistry, Organic
Sk Md Samim Akhtar, Sukanta Bar, Saumen Hajra
Summary: A proficient stereoselective aminoarylation reaction of N-cinnamylanilines was developed based on a two-step protocol involving catalytic enantioselective aziridination and subsequent 6-endo-tet Friedel-Crafts cyclization. The reaction showed excellent diastereo- and enantioselectivity in the synthesis of trans-3-amino-4-aryltetrahydroquinolines, with the potential for concise synthesis of bioactive compounds.
Article
Chemistry, Organic
Zeynep Dilsad Susam, Bilge Deniz Ozcan, Enis Kurtkaya, Erol Yildirim, Cihangir Tanyeli
Summary: In this study, bifunctional quinine-derived organocatalysts were used to catalyze the asymmetric Friedel-Crafts/S(N)2 domino reaction, resulting in enantiomerically enriched products. Density functional theory calculations were also performed to explain the stereoselectivity of the products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Yifei Qu, Xiaojia Cai, Yuzhuang Guan, Jiamin Tan, Zhangping Cai, Minyun Liu, Yasi Huang, Jinhui Hu, Wen-Hua Chen, Jia-Qiang Wu
Summary: A facile and straightforward method for the successful synthesis of difluoromethylated indole-3-carbinols, bisindolylmethanes, and indole-3-methanamines by a Friedel-Crafts reaction is developed, showing good to excellent yields, broad substrate compatibility, good functional group tolerance, and scalability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Valeria Nori, Francesca Della Penna, Emanuele Cocco, Simone Mantegazza, Gabriele Razzetti, Giuseppe Quattrocchi, Fabio Pesciaioli, Armando Carlone
Summary: This article presents a milder and greener approach to improve the synthesis of Dibenzosuberone (DBS), a key intermediate for the synthesis of active pharmaceutical ingredients (APIs) used for treating diseases related to the central nervous system. The approach involves the use of immobilized catalysts to reduce waste production.
Article
Engineering, Environmental
Wen-Hui Hu, Meng-Nan Liu, Qun-Xing Luo, Jianbo Zhang, Huiyong Chen, Long Xu, Ming Sun, Xiaoxun Ma, Qing-Qing Hao
Summary: This study investigates the influence of microscale structure of MWW zeolites on the kinetics for acylation of anisole with acetic anhydride. It is found that the acylation reaction occurs solely on the external acid sites of MWW zeolites, and the single-layer MWW (SL-MWW) exhibits higher recycle stability compared to the multiple-layer MWW (ML-MWW). The confinement effect within 12MR pockets on the surface of SL-MWW results in difficult desorption of product and small rate constant.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Zheng Tan, Long Chen, Lingyu Li, Yuzhen Li, Yao Luo, Fei Wang, Shunxi Dong, Xiaoming Feng
Summary: In this study, a practical and efficient synthesis of a-methylene-?-butyrolactones was developed using chiral N,N'-dioxide/Al-III complex as the catalyst. The key success of this transformation was the kinetic resolution of allylboration intermediate via asymmetric lactonization. Taking advantage of this method, a catalytic asymmetric total synthesis of eupomatilones 2, 5, and 6 was accomplished.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ryoya Tajima, Takaaki Saito, Takayoshi Arai
Summary: The conventional acid-catalyzed aza-Friedel-Crafts reaction of phenols with imines typically shows ortho-selectivity. However, a chiral bis(imidazolidine) pyridine (PyBidine)-Ni(OAc)(2) catalyst can switch the regioselectivity to para-selectivity. This switch is facilitated by the bulky PyBidine-Ni(OAc)(2) catalyst with a Ph2CHCH2 substituent, resulting in highly para-selective aza-Friedel-Crafts reactions (up to 99:1 para/ortho selectivity).
Review
Chemistry, Organic
Jose Clerigue, M. Teresa Ramos, J. Carlos Menendez
Summary: Catalytic asymmetric Povarov protocols have experienced explosive growth in the past decade, focusing on the use of chiral Lewis and Bronsted acids, as well as strategies involving hydrogen bond formation and covalent aminocatalysis. Recent variations, such as the nitroso Povarov reaction and interrupted Povarov reactions, are also discussed as alternative routes to chiral scaffolds beyond tetrahydroquinolines.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jie Zheng, Meng-Yu Rong, Fang-Fang Feng, Fa-Guang Zhang, Chi Wai Cheung, Jun-An Ma
Summary: In this study, the organocatalytic asymmetric aza-Friedel-Crafts-type reaction of indol-3-ones with 1- and 2-naphthols was performed using spirocyclic chiral phosphoric acids and quinine-incorporated squaramides as the organocatalysts. Two classes of structurally distinct chiral compounds, namely 2-(hydroxylnaphthyl)-indolin-3-ones and tetrahydrofuroindoles, were formed. These quaternary centre-containing indoline derivatives may have applications in the synthesis of biologically active molecules.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Samim Akhtar, Saumen Hajra
Summary: A one-pot asymmetric aminoarylation reaction has been developed for the synthesis of trans-4-amino-5-aryltetrahydrobenzo[c]azepines with excellent diastereo- and enantioselectivity. The reaction proceeds through aziridination followed by intramolecular cyclicization. A chiral indenyl bis(oxazoline) ligand is found to be effective for the catalytic enantioselective version of this one-pot transformation.
Article
Chemistry, Multidisciplinary
Yuki Saito, Shu Kobayashi
Summary: The article discusses the application of chiral heterogeneous Sc catalysts in continuous-flow reactions, achieving efficient synthesis of compounds through noncovalent interactions and the crucial role of heteropoly acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Jun-Rong Song, Zhi-Yao Li, Guang-Di Wang, Ni Zhang, Chao Chen, Juan Chen, Hai Ren, Weidong Pan
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Multidisciplinary
Shuai Pang, Xinyi Wang, Pan Wang, Yunlong Ji
Summary: The researchers reported a biomimetic, ultra-stable AORFB utilizing an amino acid functionalized phenazine, highlighting the importance of molecular engineering for robust redox-flow batteries.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Jiancong Xu, Shuai Pang, Xinyi Wang, Pan Wang, Yunlong Ji
Summary: This study demonstrates the high capacity and extreme stability of propionic-acid-functionalized phenazine (PFP) in Aqueous Organic Redox Flow Batteries (AORFBs) at both room and elevated temperatures, showing promising potential for future energy storage technology in tough conditions with high temperature and strong alkaline solutions.
Article
Chemistry, Applied
Xiao-Tong Lin, Cheng Zhao, Da-Ru Wang, Guang-Cheng Wu, Guo-Shu Chen, Shu-Jie Chen, Hai Ren, Dong-Sheng Deng, Yi-Bing Xu, Xiao-Wei Hu, Yun-Lin Liu
Summary: This study presented a BiCl3-mediated tandem cyclization reaction of tryptamine-ynamides, leading to the formation of pentacyclic spiroindoline scaffolds in moderate to excellent yields. The reaction also demonstrated the divergent synthesis of tricyclic indole derivatives with moderate yields by manipulating substrate structures, showcasing the synthetic utility of the methodology.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Zhi-Yao Li, Wei Wang, Jun-Rong Song, Rui-An Wang, Jun Shi, Qin Chi, Yan Li, Hai Ren, Wei-Dong Pan
Summary: The novel indoline scaffold was synthesized using transition metal catalysis and environmentally friendly oxidant O-2/air. Different from traditional methods, a copper-catalyzed oxidative reaction was developed and demonstrated for the synthesis of various natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shu-Jie Chen, Guo-Shu Chen, Tao Deng, Jia-Hui Li, Zhi-Qing He, Li-Shan Liu, Hai Ren, Yun-Lin Liu
Summary: This Letter presents a novel approach for the 1,2-dicarbofunctionalization of trifluoromethyl alkenes. The method involves a cascade reaction of pyridinium salts with trifluoromethyl alkenes, leading to the formation of pyridines bearing a trifluoromethyl-substituted quaternary center.
Article
Chemistry, Organic
Wei Wang, Shu-Yun Jiang, Jun-Rong Song, Wei Wu, Jun Shi, Zhi-Yao Li, Ying-Ai Wu, Qin Chi, Wei-Dong Pan, Hai Ren
Summary: The first example of cyclization cross-coupling of tryptophols and tryptamines has been achieved by copper catalysis, resulting in the direct construction of a new class of heterocyclic 3a,3a'-bisindolines. Mechanistic control experiments revealed that the copper catalyst selectively coordinates with the nitrogen moiety of the tryptamine, initiating the oxidation, and a nucleophilic-alkylation process is proposed for the carbon-carbon bond formation.
Article
Chemistry, Organic
Jun Shi, Rui-An Wang, Wei Wu, Jun-Rong Song, Qin Chi, Wei-Dong Pan, Hai Ren
Summary: This study reports a safe and convenient copper-catalyzed selective oxidation method using atmospheric oxygen as the oxidant. The method allows for the oxidative rearrangement of indole compounds, leading to the formation of various functionalized products. This represents a significant advance in the field of indole oxidation.
Article
Chemistry, Organic
Hai Ren, Ying-Ai Wu, Jun-Rong Song, Wei Wu, Xiaoyan Yang, Jun Shi, Wei-Dong Pan
Summary: Transition-metal-catalyzed C-N bond formation reactions have been extensively studied, but the site-selective intermolecular C-N cross-coupling between identical molecules is relatively unexplored. In this study, we present a highly selective copper-catalyzed oxidative cyclization/C-N cross-coupling of two tryptamines using O-2 as the terminal oxidant, providing a practical and direct route to a new class of indole-linked-pyrroloindoline compounds in moderate to good yields. Mechanistic studies revealed that the coordination between the copper catalyst and the tryptamine substrate is crucial for controlling chemoselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Lu Li, Yihang Su, Yunlong Ji, Pan Wang
Summary: In this work, a long-lived water-soluble organic radical species called PSPR was reported for bioimaging and aqueous energy storage technologies. PSPR has high solubility and stability in water, with a long lifetime due to its resistance to dimerization or disproportionation reactions and its appropriate electron density that prevents reactions with oxygen or water. PSPR also exhibits magnetic activity and ambipolar redox activity in water, making it promising for applications such as redox flow batteries.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Shu-Yun Jiang, Jun Shi, Wei Wang, Yan-Zheng Sun, Wei Wu, Jun-Rong Song, Xiaoyan Yang, Ge-Fei Hao, Wei-Dong Pan, Hai Ren
Summary: We report a copper-catalyzed selective single-electron transfer strategy for the oxidative rearrangement of 3-substituted indoles using air as the terminal oxidant. This method provides a streamlined approach to access 3-hydroxyl-, 3-alkoxyl-, and 3-hygrogenous-2-oxindoles via a 3-radical-2-hydroxyl indoline intermediate. The protocol demonstrates high chemoselectivity, good functional group tolerance, and broad application potential in the modular synthesis of biologically 3-functionalized oxindole derivatives.
Article
Chemistry, Physical
Shu-Yun Jiang, Jun Shi, Wei Wang, Yan-Zheng Sun, Wei Wu, Jun-Rong Song, Xiaoyan Yang, Ge-Fei Hao, Wei-Dong Pan, Hai Ren
Summary: A unified and efficient copper-catalyzed selective single-electron transfer strategy is reported for three oxidation reactions of 3-substituted indoles using air (O2) as the terminal oxidant, providing a streamlined and practical synthetic approach to access 3-hydroxyl-, 3-alkoxyl-, and 3-hygrogenous-2-oxindoles via a 3-radical-2-hydroxyl indoline intermediate. This copper catalysis protocol demonstrates high chemoselectivity, good functional group tolerance, and broad application potential in the modular synthesis of biologically 3-functionalized oxindole derivatives.
Article
Chemistry, Organic
Hai Ren, Rui-An Wang, Jun Shi, Jun-Rong Song, Wei Wu, Qin Chi, Ni Zhang
Summary: We report a protonic-acid-promoted electrosynthetic strategy for the dearomative dibromocyclization of tryptamine/tryptophol derivatives for the convenient late-stage 3,5-diversification of heterocyclic indolines.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ying-Ai Wu, Rui-An Wang, Shu-Yun Jiang, Tai-Bai Jiang, Jun-Rong Song, Jun Shi, Wei Wu, Wei-Dong Pan, Hai Ren
Summary: In this study, a water-mediated electrochemical synthesis method was developed for the C3/C5-bromocyclization of tryptophol and tryptamine derivatives. By controlling the amount of water, the selective synthesis of 3a- or 5a-bromoindolines was achieved without the need for additional oxidants or additives.
Article
Chemistry, Multidisciplinary
Wei Wang, Jun-Rong Song, Zhi-Yao Li, Ting Zhong, Qin Chi, Hai Ren, Wei-Dong Pan
Summary: A copper-catalyzed alkoxycyclization of tryptamine derivatives with O-2 as the oxidant has been developed, providing a variety of C3a-alkoxypyrroloindolines in good yields with high diastereoselectivities. The reaction involves a double catalytic cycle with copper-catalyzed carboamination cyclization followed by a copper-catalyzed radical alkoxylation reaction.
