Article
Chemistry, Organic
Xiao-Wen Wang, Rui-Xue Li, Yang Deng, Ming-Qiu-Hao Fu, Ya-Nan Zhao, Zhi Guan, Yan-Hong He
Summary: This article proposes a new method for the direct hydroxylarylation of unactivated benzylic carbons (sp3/sp2/sp) without the need for pre-functionalized benzylic alcohols, aromatic aldehydes, or ketones. It features direct functionalization of unactivated benzylic C(sp3)-H bonds and benzylic sp2/sp-carbons, mild conditions (open air, room temperature), an environmentally friendly procedure (without any external catalyst/mediator/additive), and direct access to sterically hindered alcohols from inexpensive and readily available alkyl/alkenyl/alkynylbenzenes. Mechanistic studies strongly support the proposed radical-radical cross-coupling between transient ketyl radicals and persistent radical anions. Gram-scale synthesis and diversification of drug derivatives demonstrate the practical potential of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hua Yao, Xiaoyang Zhong, Bingqing Wang, Sen Lin, Zhaohua Yan
Summary: A novel and efficient approach for the amine-directed dehydrogenative C(sp(2))-C(sp(3)) coupling of arylamines with acetonitrile was developed using FeCl2 as the catalyst. The method provides a straightforward and green route to arylacetonitriles with good regioselectivity and excellent compatibility of functional groups and aromatic rings.
Article
Chemistry, Multidisciplinary
Muhammad Asif Iqbal, Le Lu, Hina Mehmood, Ruimao Hua
Summary: This study reports a Cs2CO3-promoted cross-coupling reaction of arenes with cyano-/nitro-substituted aryl halides in DMSO to afford biaryls in the absence of ligands. The cyano/nitro groups in biaryls are shown to be useful for further transformations. Additionally, the formation of dibenzofurans from reactions between arenes and 1-bromo-2-iodobenzene is reported. A radical mechanism for the formation of biaryls is proposed based on control experiments and theoretical studies.
Article
Chemistry, Multidisciplinary
Mo Chen, Austin M. Ventura, Soumik Das, Ammar F. Ibrahim, Paul M. Zimmerman, John Montgomery
Summary: Current methodologies for metal-catalyzed cross-couplings require the installation of reactive functional groups on both reaction partners in advance. In contrast, C-H functionalization approaches show potential in simplifying the substrates required; however, challenges such as low reactivity and similar reactivity of different C-H bonds add complexity. This study describes an oxidative cross dehydrogenative coupling of α-amino C(sp(3))-H bonds and aldehydes to produce ketone derivatives using an unusual reaction medium that simultaneously utilizes di-tert-butyl peroxide as an oxidant and zinc metal as a reductant. The method has a broad substrate scope and offers an attractive approach for accessing α-amino ketones through the formal acylation of C-H bonds adjacent to nitrogen in N-heterocycles. Experimental investigation and computational modeling provide evidence for a mechanistic pathway involving cross-selective nickel-mediated cross-coupling of α-amino radicals and acyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xiuqi Zhang, Fukuan Zhang, Xiaolan Li, Ming-Zhu Lu, Xin Meng, Lei Huang, Haiqing Luo
Summary: This study presents an efficient rhodium(III)-catalyzed reaction, using water as a sustainable solvent, for the o-C-H arylation of readily available benzimidate derivatives with diverse arylsilanes. This method enables the straightforward synthesis of potentially useful biphenyl-2-carbonitrile derivatives. It provides an important synthetic application.
Article
Chemistry, Organic
Sumit Garai, Devarajulu Sureshkumar
Summary: In this study, a palladium-catalyzed efficient and versatile method for C(sp(2))-H ortho-cyanomethylation of arylamides with a broad substrate scope and moderate to excellent yields was developed. An inexpensive and commercially available chloroacetonitrile was used as the cyanomethylating source. The synthetic feasibility of this technique was also demonstrated by gram-scale synthesis and functional group transformation of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sumit Garai, Devarajulu Sureshkumar
Summary: In this study, a palladium-catalyzed and versatile method for ortho-cyanomethylation of arylamides with a broad substrate scope and moderate to excellent yields was developed. Chloroacetonitrile, which is inexpensive and commercially available, was used as the cyanomethylating source. The method is also compatible with the air atmosphere. Furthermore, the synthetic feasibility of this technique was demonstrated through gram-scale synthesis and functional group transformation of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Ya-Ming Tian, Evamaria Hofmann, Wagner Silva, Xiang Pu, Didier Touraud, Ruth M. M. Gschwind, Werner Kunz, Burkhard Koenig
Summary: The amino alcohol meglumine solubilizes organic compounds in water and enforces the formation of electron donor acceptor (EDA) complexes, resulting in unique cross-coupling reactions. UV-A photoinduced electron transfer within the EDA complexes leads to the cleavage of halide ions and recombination of arenes, followed by rearomatization and proton loss. UV and NMR measurements demonstrate the significance of the EDA aggregates for the photoinduced reaction. Enforced EDA aggregate formation in water provides new activation modes for organic photochemical synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hidenori Matsuyama, Xuan Zhang, Masahiro Terada, Tienan Jin
Summary: A versatile method for synthesizing alkylidene fluorenes and their heteroarene derivatives has been successfully developed by using a Pd(II)-catalyzed direct C-H/C-H coupling of o-alkenyl biaryls. Under aerobic oxidation conditions, the use of Pd(OAc)2 catalyst produces alkylidene fluorenes with various functional groups and diverse polycyclic systems. These resulting products can be utilized as versatile synthetic building blocks for constructing structurally diverse polycyclic arenes and heteroarenes.
Article
Chemistry, Applied
Meng-Meng Guo, Gan-Qi Qin, Xin-Yu Jiang, Hao Xu, Mengtao Ma, Zhi-Liang Shen, Xue-Qiang Chu
Summary: This study presents a metal-free, catalyst-free, and additive-free aerobic coupling reaction of benzhydryl phosphonium salts with simple alkenes to access trisubstituted olefins. The C(sp(3))-C(sp(2)) bond is formed through the functionalization of C-P and C-H bonds using O-2 as a green oxidant and DMSO as a promoter. The method demonstrates a broad substrate scope and synthetic potential, with the 1,3,5-trimethoxybenzene fragment in the resulting products proving to be feasible for further transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Shiyi Yang, Hengzhao Li, Xiang Yu, Jie An, Michal Szostak
Summary: A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using a very low loading of [Pd] in the presence of mild K3PO4 base under aqueous conditions. This operationally trivial protocol allows for the activation of C-O bond and is tolerant to various sensitive functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Victoria Dimakos, Daniel P. Canterbury, Sebastien Monfette, Philipp C. Roosen, Stephen G. Newman
Summary: This study describes a Pd-catalyzed method for the direct and selective alpha-arylation of cyclic enones using (hetero)aryl triflates. Optimized ligands and additives were employed to achieve high selectivity. Preliminary mechanistic investigations suggest that the reaction proceeds through enone activation and Pd-catalyzed enolate arylation, resembling a Morita-Baylis-Hillman reaction.
Review
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Antoine de Gombert, Janette McKnight, Loic R. E. Pantaine, Michael C. Willis
Summary: This review focuses on the methods developed for the challenging coupling of 2-pyridine nucleophiles with (hetero)aryl electrophiles, ranging from traditional cross-coupling processes to alternative nucleophilic reagents and novel main group approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Pan-Pan Guo, Zhen-Hong He, Shao-Yan Yang, Weitao Wang, Kuan Wang, Cui-Cui Li, Yuan-Yuan Wei, Zhao-Tie Liu, Buxing Han
Summary: In this study, Cu-Zr bimetallic catalysts were prepared and evaluated for CO2 reduction reaction. Among them, the Cu-Zr catalyst showed excellent ethene production rate and high current density in 0.1 M KCl electrolyte. Experimental and computational analysis revealed that the interface interaction between Zr and Cu contributes to the enhanced performance of the catalyst.
Review
Materials Science, Multidisciplinary
Zhong-Yu Wang, Zhen-Hong He, Long-Yao Li, Shao-Yan Yang, Meng-Xin He, Yong-Chang Sun, Kuan Wang, Jian-Gang Chen, Zhao-Tie Liu
Summary: CO2-ODHP is an attractive strategy for reducing CO2 emissions and offsetting the propylene demand gap. The introduction of CO2 improves the stability of oxidation active sites, increases propane conversion, and extends the catalyst's lifetime. However, the development of environmentally friendly and chromium-free catalysts remains challenging.
Article
Chemistry, Multidisciplinary
Weitao Wang, Huan Wang, Xulu Jiang, Zhen-Hong He, Yang Yang, Kuan Wang, Zhao-Tie Liu
Summary: In this study, zirconium-based catalysts were prepared and successfully used to convert HMF into BPMF with a high yield of 92.4% in a one-pot strategy. The mechanism of the reductive etherification reaction was also investigated.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Nanoscience & Nanotechnology
Yingying Zhang, Guanglin Fan, Jinqiang Jiang, Zhaotie Liu, Zhongwen Liu, Guo Li
Summary: This study reports the development and regulation of gradient structures of hydrogels for programmable thermally responsive actuating behaviors. The shapes and actuation amplitudes of the hydrogel actuators can be independently regulated by controlling the formation and photodissociation of Fe3+-carboxylate coordination in the formed gradient networks. Some interesting applications have been realized, demonstrating the potential for extending this method to other hydrogel actuators with different compositions and stimuli-responsive behaviors.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Long-Yao Li, Zhong-Yu Wang, Shao-Yan Yang, Jian-Gang Chen, Zhen-Hong He, Kuan Wang, Qun-Xing Luo, Zhong-Wen Liu, Zhao-Tie Liu
Summary: In this study, Fe-doped silicalite-1 zeolite was used as a matrix to implant GaN nanocrystallites. The incorporation of isolated framework Fe atoms resulted in the generation of more interior silanols and silanol nests, leading to the formation of highly dispersed GaN nanocrystallites embedded in the Fe-silicalite-1 matrix. The particle size distribution of GaN could be adjusted by regulating the molar ratio of Si/Fe.
Article
Chemistry, Multidisciplinary
Weitao Wang, Liqiong Ma, Xulu Jiang, Huan Wang, Zhen-Hong He, Kuan Wang, Yang Yang, Zhao-Tie Liu
Summary: This study developed a new approach for the cyanide-free synthesis of organic nitriles through highly direct oxidative cyanation of alcohols. By using a CoOx/MnO2 catalyst under aqueous ammonia conditions, benzyl alcohol was successfully converted to benzonitrile with high yield and selectivity. Kinetic studies revealed that the oxidation of benzyl alcohol was the rate-determining step in the consecutive reactions. The catalytic system also demonstrated its applicability to various types of alcohol substrates, showcasing a sustainable synthesis strategy.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Inorganic & Nuclear
Junlei Wang, Kuan Wang, Zhen-Hong He, Tong Sun, Run-Jing You, Jian-Gang Chen, Weitao Wang, Yang Yang, Zhao-Tie Liu
Summary: Bi2WO6 with double active sites of tunable metallic Bi and oxygen vacancies (OV-Bi/Bi2WO6) was prepared by solvothermal treatment and used as an efficient photocatalyst for the partial oxidation of cyclohexane (CHA) to cyclohexanone (CHA-one) in air. The Bi : Bi2WO6 ratio in OV-Bi/Bi2WO6 could be tailored by controlling the solvothermal temperature, and the synergistic effect between DMF and EG increased the reduction of MDF/EG and promoted the production of Bi. OV-Bi/Bi2WO6 showed significantly enhanced photocatalytic activity attributed to its specific surface area, photo-absorption, oxygen vacancies, and efficient electron-hole separation.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Yang Yang, Qian-Nan Yang, Yi-Bin Yang, Peng-Fei Guo, Wan-Xin Feng, Yan Jia, Kuan Wang, Wei-Tao Wang, Zhen-Hong He, Zhao-Tie Liu
Summary: Designing a highly active single atom catalyst, particularly noble-metal atoms in two-dimensional LDH nanostructures, is essential for speeding up the slow oxygen evolution reaction (OER). By reducing a solution, Ru single atoms (SAs) are fixed on NiFe LDH to form SARu/NiFe LDH. The activity evaluation shows that SARu/NiFe LDH exhibits higher activity and Faradaic efficiency compared to pure NiFe LDH.
Article
Nanoscience & Nanotechnology
Ling Hu, Jinqiang Jiang, Zhao-Tie Liu, Zhong-Wen Liu, Guo Li
Summary: A simplified treatment process is reported to convert 2D poly(ethylene oxide)/sodium alginate/tannic acid thin films into 3D-shaped moisture- and NIR light-responsive actuators. Wetting the film surface releases residual stress in a gradient manner, driving the wetted regions to bend bidirectionally. A gradient cross-linking network formed by Fe3+ ions and sodium alginate chains stabilizes the resulting 3D shape and provides moisture-responsive morphing behaviors. Fe3+ ions also enable the film to respond to NIR light by self-assembling with tannic acid molecules. Films with versatile 3D shapes and deformation modes can be conveniently fabricated using this one-step treatment process.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Nanoscience & Nanotechnology
Xiangxi Cui, Min Dang, Jinqiang Jiang, Zhao-Tie Liu, Zhong-Wen Liu, Guo Li
Summary: In this study, a photoresponsive elastic composite is developed, which can be programmed and transformed into different shapes through UV light irradiation and stretching. The composite exhibits adjustable shape and strain-sensitive conductivity, which opens up possibilities for designable soft electronics.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Nanoscience & Nanotechnology
Weitao Wang, Liqiong Ma, Huan Wang, Xulu Jiang, Zhen-Hong He, Kuan Wang, Yang Yang, Lu Li, Zhao-Tie Liu
Summary: In this study, a Se,P,N-tridoped carbon nanomaterial (Se,P,N/CN-900) was successfully prepared and used as a metal-free catalyst for the direct ammoxidation of alcohols to nitriles with aqueous ammonia and molecular oxygen. The tridoped carbon catalyst exhibited highly efficient catalytic performance and good stability, enabling the conversion of various (hetero)aromatic alcohols to corresponding nitriles with high yields. To the best of our knowledge, this is the first work to achieve ammoxidation of alcohols to nitriles with a high efficiency over multidoped carbon materials.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Physical
Yang Yang, Qian-Nan Yang, Yi-Bin Yang, Peng-Fei Guo, Wan-Xin Feng, Yan Jia, Kuan Wang, Wei-Tao Wang, Zhen-Hong He, Zhao-Tie Liu
Summary: Designing and synthesizing highly active single atom catalysts, especially monodispersed noble-metal atoms fixed in two-dimensional layered double hydroxide (LDH) nanostructures, is crucial for accelerating the slow oxygen evolution reaction (OER). In this study, Ru single atoms (SAs) were stabilized on NiFe LDH (SARu/NiFe LDH) via an oxygen-coordinated bond after a facile solution reduction procedure. The SARu/NiFe LDH exhibits higher activity than pure NiFe LDH in basic media, with 99.3% Faradaic efficiency based on rotating ring-disk electrode measurement. This study provides a general avenue for developing efficiently monoatomic and even multiatomic catalysts in the future.
Review
Chemistry, Physical
Yukun Ruan, Zhen-Hong He, Zhao-Tie Liu, Weitao Wang, Leiduan Hao, Liang Xu, Alex W. Robertson, Zhenyu Sun
Summary: This review summarizes the important progress in the electroreduction of N2 to NH3 using state-of-the-art two-dimensional (2D) electrocatalysts. Several reaction mechanisms of nitrogen reduction reaction (NRR) are explained, and recent experimental progress regarding these unique 2D NRR electrocatalysts is reported. Furthermore, concepts proposed from high-throughput computations and machine learning are described. By understanding the N2 conversion to NH3 process on 2D electrocatalysts, novel 2D materials that could potentially serve as viable NRR electrocatalysts are presented. The future perspectives and challenges of N2 electrolysis using 2D materials are also discussed.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Zhen-Hong He, Cui-Cui Li, Shao-Yan Yang, Jiajie Liu, Hui-Hui Cao, Kuan Wang, Weitao Wang, Yang Yang, Zhao-Tie Liu
Summary: In this study, a series of easily prepared CuOx catalysts were developed and applied in CO2 electrocatalytic reduction to synthesize ethylene; the introduction of neodymium stabilizes the catalyst and enhances CO2 adsorption; coupling *CO with ethylene further improves the Faradaic efficiency of ethylene.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Physical
Yukun Ruan, Zhen-Hong He, Zhao-Tie Liu, Weitao Wang, Leiduan Hao, Liang Xu, Alex W. Robertson, Zhenyu Sun
Summary: “This review summarizes the significant progress in electroreduction of N2 to NH3 using state-of-the-art two-dimensional (2D) electrocatalysts. Several reaction mechanisms of NRR are explained and recent experimental progress on these unique 2D NRR electrocatalysts is reported. Additionally, concepts proposed from high-throughput computations and machine learning are discussed. Novel 2D materials that have the potential to serve as viable NRR electrocatalysts are presented based on a detailed understanding of the N2 conversion process on 2D electrocatalysts. Future perspectives and challenges of N2 electrolysis using 2D materials are also addressed.”
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
