2025-62
Facile Synthesis of 2D Metal-Organic Framework as an Efficient Heterogeneous Catalyst for the Epoxidation of Olefin With H2O2
Yan Cai, Wei Yang, Ali Morsali, Chunyan Zhang, Zhengguo Zhang, Guoying Zhang
Chemistry – A European Journal 2025. https://doi.org/10.1002/chem.202503019
Abstract:
The 2D ultrathin MOF nanosheets, which effectively integrate metals and functional ligands, possess the advantageous features of molecular catalysts and exhibit remarkable catalytic activity in multiphase catalysis. Herein, we employed the sacrificial template method to achieve in situ attachment of metalloporphyrin onto a ZnO substrate, resulting in the formation of surfactant-free 2D dispersed structures of Zn-TCPP(Mn)/ZnO. The multilayered stacked B-Zn-TCPP(Mn) (3D) blocks were prepared by growing Zn2+ mixed with metalloporphyrin as a comparison. The novel composite catalyst Zn-TCPP(Mn)/ZnO was employed for the efficient epoxidation of various alkenes using H2O2 as an oxidant at ambient temperatures. Notably, alkenes conversion within 20 min achieves a high yield and impressive 1980 h−1 turnover frequency. The composite catalyst can still maintain its structural integrity after undergoing five consecutive cycles, and the total yield of oxidized styrene is slightly reduced. This was confirmed by a series of characterization analyses and other assessments. Additionally, comparative experiments revealed that the B-Zn-TCPP(Mn) blocks underwent partial exfoliation into 2D nanosheets following the catalytic reaction, thereby enhancing the catalytic conversion efficiency in subsequent epoxidation reactions. This finding provides compelling evidence for the heightened catalytic activity of 2D materials.
2025-61
A pyrazole ligand improves the efficiency of Mn-catalysts for transfer hydrogenation
Cai, Yan, Li, Xiulin, Zhang, Zhengguo, Ramezani Ali, Morsali Ali, Zhang, Guoying
New J. Chem., 2025,49, 3020-302410.1039/d4nj05028b
Abstract:
The high cost associated with noble metal catalysts has led to a surge in interest towards harnessing the abundant 3Dmetals as catalysts for catalytic hydrogenation.Many 3Dmetal catalysts have been disclosed in recent years for transfer hydrogenation reactions, but the reported catalyst metal loads are too high compared to precious metal catalysts, sometimes up to three orders of magnitude higher. Therefore, it is necessary to solve the actual coordination of ligands and metals in non-preciousmetal catalysts and avoid excessive consumption of transition metals and ligands, in order to realize the effective practical application of 3D metal catalytic systems in various industries. A practical and scalable catalytic system employing pyrazole ligands coordinated to Mn is introduced for transfer hydrogenations. By means of pre-activation via dehydrohalogenation, an efficient and unprecedented Mn–N2 catalytic system has been established, showcasing exceptional tolerance towards a diverse array of functional groups and enabling broad application across a wide range of alcohols. Significantly, this protocol facilitates the facile synthesis of multiple pharmaceuticals within a single reaction vessel.
2025-60
Optimizing Mn/SiO2 catalyst for additive - free epoxidation of long - chain α -olefins in air
Fangchao Wang a b, Rui Liu a b, Hongyi Cui a b, Ali Ramazani c, Ali Morsali d, Guoying Zhang a
Applied Catalysis A: General Volume 700, 25 June 2025, 120288. https://doi.org/10.1016/j.apcata.2025.120288
Abstract:
The epoxidation of long-chain α-olefins presents a significant challenge in synthetic chemistry, particularly when employing molecular oxygen from air as the sole oxidant under additive-free conditions. In this study, we demonstrate that manganese supported on mesoporous silica (Mn/MSN) effectively catalyzes the aerobic epoxidation of long-chain α-olefins without requiring initiators or sacrificial agents. Mechanistic investigations reveal a synergistic interplay between Mn(II) and Mn(III) species, which facilitates the selective cleavage the peroxo bonds (O–O) in alkyl hydroperoxide intermediates. Strategic incorporation of iron and zirconium into the Mn/MSN framework modulates the manganese oxidation states, enriching the Mn(II)/Mn(III) ratio and achieving a remarkable space-time yield of up to 200 mol epoxide mol⁻¹Mn h⁻¹ . Radical trapping experiments combined with high-resolution mass spectrometry corroborate the formation of allyl carbon-centered and alkoxy radical intermediates during the reaction. This work provides a feasible strategy for long-chain α-olefin aerobic epoxidation without any additives.
2025-59
Reagent-assisted regio-divergent cyclization synthesis of pyrazole
Mengdi Pang,ab Ali Ramazani, 
c Zhengguo Zhang*ad and Guoying Zhang *b
Org. Biomol. Chem., 2025, 23, 2812–2817. https://doi.org/10.1039/D5OB00030K
Abstract:
The present study reveals a practical one-pot base-promoted regio-divergent cyclization of hydrazines with alkynyl silane under mild conditions, facilitating the synthesis of diverse silicone-substituted pyrazoles and functionalized pyrazoles in great yields with exceptional selectivity. This protocol is expected to afford a streamlined one-pot approach for the synthesis of multiple compounds in water.
2025-58
Recent Progress of Platinum and Rhodium Catalysts in Hydrosilylation Reactions
Leila Mirghaffari, Seyedmohammad Hosseininezhad, Melika Seydi, Ali Ramazani, Hamideh Ahankar, Guoying Zhang
ChemistrySelect, 2025, e202501079. https://doi.org/10.1002/slct.202501079.
2025-57
Development of a self-driven electron transfer metal-organic framework for reactive oxygen species (ROS) generation in GSH-depleted cancer therapy
Somayeh Tarasia, Sina Pirani Ahmad Abada, Ali Ramazania, b, c, ⁎, Ali Morsalid, **, Guoying Zhang ***
Abstract:
This study presents the design of a system based on metal-organic frameworks engineered, enabling the generation of reactive oxygen species (ROS) by self-driven electron transfer without requiring external stimulation. By simultaneously depleting intracellular glutathione (GSH), this approach enhances the specific treatment of cancer cells with heightened efficiency. For this investigation, a zirconium-based MOF (MOF-801) was chosen as the carrier for Bi nanoparticles due to its outstanding properties and biocompatibility. The mechanism of this process relied on the significantly lower standard potential of Zr compared to Bi, enabling the system to produce ROS through the spontaneous transfer of electrons from Bi nanoparticles to MOF-801. The Results showed that Bi NPs act as electron donors and electrons flow to MOF-801 spontaneously due to the formed Schottky barrier when they are in contact. The increase in electron density facilitated by Bi@MOF-801 in the presence of oxygen results in the formation of O2−, H2O2, and OH. In vitro anticancer studies also demonstrated that Bi@MOF-801 was capable of effectively destroying approximately %60 of MDA-MB-231cells (Breast cancer cell line). In addition, validation was provided by a live/dead cell staining assay. The percentage of apoptotic cells in the Bi@MOF-801 group reached 24.4 %, significantly higher than in the MOF-801 (1.84 %) and Bi ion (0.54 %) groups. The results showed that the fabricated nano-agent, without the need for external stimulation like radiation or temperature, could function as a ROS amplifier by depleting GSH, thereby enhancing therapeutic performance.
2025-56
Sustainable synthesis of a mixed-metal MOF: avisible light responsive photocatalyst for theselective oxidation of benzyl alcohols
Hosein Ghasempour, Farnoosh Zarekarizi, Behnam Habibi, Guoying Zhang,⁎ Ali Ramazani and Ali Morsali
CrystEngComm, 2025,27, 4826-4834https://doi.org/10.1039/D5CE00302D (IF:xx/1Q/TOP)
Abstract:
This study presents an efficient and innovative allylation strategy utilizing C/N/O nucleophilic reagents with attenuated reactivity, enabling the construction of versatile allyl compounds. The approach focuses on the sequential allylation of dihalides in large-scale chemical manufacturing, effectively addressing the challenge of achieving selectivity in cascade reactions. The methodology is centered on the Cu-catalyzed C-olefination of alkynes with dihalides, significantly expediting the synthesis of a diverse array of finely conjugated enyne derivatives. Furthermore, a base-facilitated sequential condensation process has been developed to achieve the N-allylation of hydrazines, yielding a wide range of trisubstituted alkenyl hydrazones. Additionally, the protocol enables the synthesis of high-value ester compounds through O-allylation or esterification with dihalides. This transformation also facilitates the one-step synthesis of a variety of essential pharmaceuticals, demonstrating its broad synthetic utility and potential.
2025-55
Efficient Allylation of Dihalides: A Versatile Approach to C/N/O-Functionalized Derivatives
Mengdi Pang, Wentao Hao, Xiulin Li, Chunyan Zhang, Ali Morsali, Ali Ramazani, Guoying Zhang⁎
Chin. J. Chem., 2025, 43. 2005-2041 (IF:5.456/1Q/TOP) DOI: 10.1002/cjoc.70084
Abstract:
This study presents an efficient and innovative allylation strategy utilizing C/N/O nucleophilic reagents with attenuated reactivity, enabling the construction of versatile allyl compounds. The approach focuses on the sequential allylation of dihalides in large-scale chemical manufacturing, effectively addressing the challenge of achieving selectivity in cascade reactions. The methodology is centered on the Cu-catalyzed C-olefination of alkynes with dihalides, significantly expediting the synthesis of a diverse array of finely conjugated enyne derivatives. Furthermore, a base-facilitated sequential condensation process has been developed to achieve the N-allylation of hydrazines, yielding a wide range of trisubstituted alkenyl hydrazones. Additionally, the protocol enables the synthesis of high-value ester compounds through O-allylation or esterification with dihalides. This transformation also facilitates the one-step synthesis of a variety of essential pharmaceuticals, demonstrating its broad synthetic utility and potential.
2025-54
Indazole enhances Ru-catalyzed hydrogenation of unsaturated bonds
Wenjun Jiang,a,b Xiulin Li,a Yaru Liu,b Chunyan Zhang,c Guoying Zhanga* & Ali Morsalid
Org. Chem. Front., 2025, 12. 1936-1944. (IF:5.456/1Q/TOP) https://doi.org/ 10.1039/d4qo02176b
Abstract:
The catalytic hydrogenation process is highly coveted and presents a formidable challenge due to its efficient conversion of crucial molecules into environmentally friendly alcohols, showcasing exceptional atom efficiency and selectivity. Moreover, these alcohol products serve as versatile precursors for synthesizing various pharmaceutical compounds. Herein, we have developed a practical and efficient procedure for the hydrogenation of various unsaturated compounds using Ru-catalysis with an indazole backbone PNN pincer ligand. This groundbreaking method effectively tackles the challenge of chem-selectivity in multifunctional hydrogenation reactions involving C=C/N/O bonds. The Ru catalytic system exhibits exceptional performance in the scalable synthesis of PNN ligands, achieving an astonishing turnover number (63,371) and producing an impressive 146.18 grams of alcohol with a catalyst concentration as low as 0.001 mol%. Importantly, the protocol holds immense significance as it enables the convenient one-pot synthesis of multiple pharmaceuticals and facilitates the degradation of waste polymers.
2025-53
Recent advances in COF-derived carbon materials: Synthesis, properties, and applications
Yaqin Zhu, Lizhen Chen, Junjie Pan, Shaohua Jiang*, Jiaxiu Wang*, Guoying Zhang*, Kai Zhang*
Progress in Materials Science 2025, 101373. Doi:https://doi.org/10.1016/j.pmatsci.2024.101373.(IF:33.6/1Q/TOP)
Abstract:
Functional porous carbon materials are at the forefront of current research due to their exceptional properties, making them highly sought after for various applications, including energy storage/conversion, sensing, adsorption, and catalysis. One crucial factor in producing carbon materials with specific uses and optimized functions is the selection of appropriate carbon precursors. Covalent organic frameworks (COFs) have emerged as game-changing precursors due to their adaptable molecular design and adjustable structures. As a result, they exhibit tremendous potential for the development of advanced carbon materials. In recent years, there has been remarkable progress in COF-derived carbon materials, and we try to comprehensively cover COF-derived carbon materials from their synthetic methods to specific applications. Focusing on the relationship between structure and properties in COF-derived carbon materials, mechanism during carbonization, morphology control strategies, and properties modulation approaches are highlighted, followed by their representative applications in the last 10 years. Moreover, despite the significant advances achieved to date, COF-derived carbon materials still suffer from some limitations. Thus, proposals on how to improve COF-derived carbon materials’ performance are also discussed, as well as future challenges and perspectives, aiming to provide concise yet informative guidelines for choosing suitable carbon materials for particular applications.
2024-52
Sulfate-modified iron oxide catalyzed epoxidation of styrene with CO2 activated hydrogen peroxide in water
Fangchao Wang, Wei Yang, Ding Ding, Hongyi Cui, Guoying Zhang*
Catalysis Science & Technology 2024,14, 4704-4715. Doi:https://doi.org/10.1039/D4CY00728J.(IF:6.17/2Q/TOP)
Abstract:
Styrene oxide is a significant organic intermediate with promising applications in fine chemicals, pharmaceuticals and materials. In this study, we have developed a practical sulfate-modified iron oxide promoted epoxidation of styrene catalytic system using hydrogen peroxide as the oxidant in a solvent-free environment. The sulfate-modified iron oxide has demonstrated significant enhancement of the styrene epoxidation process with the assistance of tetrabutylammonium, resulting in a more than 10-fold increase in the yield of styrene oxide compared to the unmodified one. Mechanistic studies have revealed that hydrogen peroxide is activated by carbon dioxide and the key intermediate singlet oxygen (1O2) has been detected by electron paramagnetic resonance. Sulfur, primarily present as chelated bidentate SO42-, acts synergistically with neighbouring coordinatively unsaturated iron atoms to promote the adsorption of 1O2 on the surface and facilitate oxygen atom transfer to styrene.
2024-51
Palladium-catalyzed Multicomponent Carbonylation of Halides to Acylhydrazones
Qianqian Liang, Shuo Gao, Wentao Hao, Guoying Zhang*
The Journal of Organic Chemistry 2024, 89, 12, 8537-8545 Doi:https://doi.org/10.1021/acs.joc.4c00451.(IF: 4.198/2Q/TOP)
Abstract:
The current methods for synthesizing acylhydrazones are limited by their multistep processes, narrow substrate scope, low selectivities and poor yields. Herein, a fundamentally novel approach to bioactive acylhydrazones was developed based on the palladium-catalyzed multicomponent tandem condensation carbonylation of halides with aldehydes and hydrazines. This method provides a useful and efficient strategy for generating gram amounts of various acylhydrazones in one pot manner. Mechanistic studies provided evidence of facile carbonylation of halides with the weak nucleophile hydrazones is facilitated by base.
2024-50
Co-Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters
Shuo Gao,‡ Wentao Hao,‡, Yuqi Ji, Xiulin Li, Chunyan Zhang, and Guoying Zhang*
Chin. J. Chem. 2024, 10.1002/CJOC.202400481. (IF:5.6/1Q/TOP)
Abstract
Catalytic dehydrogenation, with its exceptional atom economy and chemo selectivity, offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules. Furthermore, the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications. The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters, facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones. We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols, and propose a plausible reaction mechanism supported by control experiments and labeling studies. Notably, it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.
2024-49
Wenjun Jiang,‡ Mengdi Pang,‡ Yan Cai,‡ Guohui Zhang, Yaru Liu* and Guoying Zhang*
Org. Chem. Front., 2024,https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00651h. (IF:5.456/1Q/TOP)
Abstract: Catalytic carbonylation, which converts multiple green or sustainable starting materials to critical compounds with high atom-economy and chemoselectivity, is a highly desirable and elusive process. Furthermore, carbonylations of alkenes with hydrazines are performed to produce acylhydrazones, which are versatile building blocks for the formation of numerous pharmaceuticals. However, the syntheses of functionalized acylhydrazones involve multi-step reactions that require harsh conditions. Therefore, we herein report practical one-pot catalytic hydrohydrazono-carbonylation condensations of alkenes with hydrazines and aldehydes to form acylhydrazones, with water as the sole coproduct, overcoming the challenge of regioselectivity in multicomponent reactions. Using appropriate ligands, branched or linear N-alkyl-substituted acylhydrazones may be obtained in good-to-high yields with excellent regioselectivities. All the acylhydrazone derivatives are unknown compounds and gram-scale (255.8 g) acylhydrazones are prepared using this protocol, and a possible reaction mechanism is proposed based on control experiments and labeling studies.
2024-48
MOF@wood derived ultrathin carbon composite film for electromagnetic interference shielding with effective absorption and electrothermal management
Xiaofan Ma, Siyuan Liu, Heng Luo, Hongtao Guo, Shaohua Jiang*, Gaigai Duan, Guoying Zhang*, Jingquan Han, Shuijian He, Wei Lu, Kai Zhang*
Adv. Funct. Mater. 2024, 34, 2310126. doi/10.1002/adfm.202310126 (IF:19.2/1Q/TOP)
Abstract
Recently, there has been a growing demand for ultra-thin carbonized wood films (CWF) with high shielding efficiency (SE) to replace non-renewable alternatives. Researchers aim to enhance electromagnetic (EM) wave absorption and improve electromagnetic interference (EMI) SE in CWF materials to reduce secondary pollution from reflected EM waves. In this work, the carbonized wood composite film (CWF/EP/Co) with a thickness of 120 µm through the process of hot-pressing and carbonizing wood soaked in a mixed solution of water-borne epoxy (EP) and Co/Zn-MOF (ZIF-67/8) is obtained. The CWF/EP/Co film exhibits excellent conductivity (105 S cm−1) and demonstrates an excellent EMI SE (73 dB) at a 200 µm thickness. Remarkably, the specific EMI shielding effectiveness (SSE/t) of CWF/EP/Co films reached 15833.3 dB·cm2·g−1 in the X-band, making it the highest reported value among all wood-derived EMI shielding materials. CWF/EP/Co films have a high absorption coefficient (A) of 0.4, indicating their effectiveness in absorbing EM waves. Furthermore, the EMI shielding effect of the large-scale wallpaper (170 mm×170 mm) is confirmed by finite element analysis. Additionally, the CWF/EP/Co film exhibits good mechanical properties and effective Joule heating performance. This shielding film shows promise in applications such as buildings and smart homes, providing EMI shielding and warming effects.
2024-47
A sustainable metal-free and additive-free olefination route to N-heteroazaarenes from methyl-substituted heterocycles and amines
Hongyi Cui, Chunyan Zhang,* Yuqi Ji, Guoying Zhang*
RSC Adv., 2024,14, 4339-4344. (IF: 4.036/3Q/TOP)
Abstract: A green and sustainable metal-free, additive-free olefination approach is proposed for the facile synthesis of various unsaturated N-heteroazaarenes from simple methyl-substituted heteroarenes and amines. The developed protocol employs only air as the sole oxidant and provides a useful strategy for obtaining various E-selective conjugated heterocycle olefins. This provides a useful strategy for application in generating grams of a varity of unsaturated N-heteroazaarenes (up to 20.33 gram) and the synthetic imaging agents of STB-8 (2.40 gram) with high regioselectivity in one pot.
2024-46
Construction of trisubstituted hydrazones via base-mediated cas-cade condensation N-alkylation
Wentao Hao, Shuo Gao, Hongyi Cui, Ding Ding, Shaohua Jiang, Chunyan Zhang*, Yuqi Ji, and Guoying Zhang*
The Journal of Organic Chemistry 2024, 89, 4, 2605-2621 . Doi:.(IF: 4.198/2Q/TOP)
Abstract: A practical base promoted tandem condensation N-alkylation reaction for the formation of trisubstituted hydrazones has been developed employing aldehydes and hydrazines with alkyl halides. Crucially, this reaction successfully overcomes chemoselectivity problems, allowing the reaction of multiple components in a one-pot manner. Halo- and hetero-functional groups, as well as free hydroxyl and amino groups, are tolerated in this transformation to produce a wide range of trisubstituted hydrazones in good to excellent yields.
2024-45
Formation of ylidenehydrazines enabled by manganese-catalyzed acceptorless dehydrogenative coupling
Fangchao Wang, Ding Ding, Chunyan Zhang*, Guoying Zhang*
Org. Chem. Front., 2024,11, 1420-1429. (IF:5.456/1Q/TOP)
Abstract: Catalytic dehydrogenation, which exhibits highly atom-economical and chemo-selective properties, converts multiple green sustainable alcohols to critical molecules and is a highly desirable and elusive process; furthermore, the dehydrogenation of alcohols with hydrazines produces ylidenehydrazines, which are versatile building blocks in the formation of numerous pharmaceuticals. However, the syntheses of functionalized ylidenehydrazines involve multi-step reactions that require harsh conditions. Herein, we report a practical one-pot catalytic tandem dehydrogenative condensation coupling of hydrazines with alcohols and halides to form ylidenehydrazines via an acceptorless dehydrogenative coupling strategy, overcoming the challenge of selectivity in multicomponent reactions. The system is based on the Earth-abundant metal Mn, which is stabilized by a novel bench-stable PNN pincer ligand derived from aminoindazole. A large series of functionalized ylidenehydrazines is obtained in high yields with excellent selectivities, and gram-scale ylidenehydrazines are prepared using this protocol. Notably, using this protocol, several pharmaceuticals may be easily synthesized in a one-pot manner. This strategy significantly broadens the scope of Mn-catalyzed dehydrogenative condensation coupling for synthesizing unsaturated molecules.
2024-44
Palladium-catalyzed allylation and carbonylation: access to allylhydrazones and allyl acylhydrazones
Qianqian Liang, Yan Cai, Wenjun Jiang, Mengdi Pang, Liming Fan and Guoying Zhang*
Chem. Commun., 2024,60, 1638-1641. DOI: https://doi.org/10.1039/D3CC05531K. (IF:6.065/2Q/TOP)
Abstract: A palladium-catalyzed allylation of hydrazines with allyl alcohols and aldehydes was developed, enabling the syntheses of a series of allylhydrazones in good to excellent yields with high regioselectivity. Furthermore, the four-component tandem allylation carbonylation of hydrazines with allyl alcohols and aldehydes was established using the catalytic system, producing various allyl acylhydrazones. Additionally, the functionalized allyl acylhydrazones could be smoothly constructed with the catalytic system employing allylhydrazones as a partner. The catalytic system exhibited good functional tolerance with excellent regioselectivities and scaled-up capability, overcoming the limitations of chemoselectivity of the multicomponent transformation and poor conversion of the weak nucleophile.
2024-43
Electrospun nanofiber nonwovens and sponges towards practical applications of waterproofing, thermal insulation, and electromagnetic shielding/absorption
Shujing Li , Gaigai Duan, Guoying Zhang* , Haoqi Yang*, Haoqing Hou , Yunqian Dai , Yueming Sun , Shaohua Jiang*
Materials Today Nano 2024, 25, 1005452. DOI: org/10.1016/j.mtnano.2024.100452. (IF:13.364/1Q/TOP)
Abstract: As a versatile and efficient technology, electrospinning is a powerful method for the fabrication of nanofiber nonwovens and sponges with high porosity, low density, and large specific surface area, which have great potential for numerous applications. In this review, the working mechanisms, preparation, and modification methods, as well as recent progress of nanofiber nonwovens and sponges towards waterproofing, thermal insulation, and electromagnetic (EM) shielding/absorption have been systematically discussed. More prominently, this review provides some insightful perspectives of electrospinning technology toward practical applications covering the range from nanofibers to nanofiber-based sponges. Expectantly, our review will offer important and thoughtful guidance not only for the rational design of nanofiber nonwovens and sponges but also for practical applications in the foreseeable future.
2023-42
Two Chemorobust Cobalt(II) Organic Frameworks as High Sensitivity and Selectivity Sensors for Efficient Detection of 3-Nitrotyrosine Biomarker in Serum
Cryst. Growth Des. 2023, 23, 11, 7716–7724. (IF:4.013/1Q/TOP)
Abstract: Rapid detection of the 3-nitrotyrosine (3-NT) biomarker in serum is of great significance in clinical diagnosis and daily disease monitoring. In this work, two chemorobust 3D metal–organic frameworks (MOFs) of [Co(DBrTPA)(NMP)]n (CoMOF-1) and [Co5(DBrTPA)4(DMF)6(HCOO)2]n (CoMOF-2) were fabricated from a halogen-modified ligand of 2,5-dibromoterephthalic (H2DBrTPA) and cobalt(II) clusters under solvothermal conditions. The introduction of halogens can improve the stability of the overall framework in different media and pH environments, which also endow two CoMOFs with great potential as luminescent sensors with high sensitivity and selectivity, fast response, good anti-interference, as well as recyclable performance in detecting 3-NT in a PBS buffer solution through quenching effects, with the Ksv values being 9.19 × 104 M–1 for CoMOF-1 and 1.05 × 105 M–1 for CoMOF-2 and the LODs as low as 23.6 ng·mL–1 for CoMOF-1 and 20.1 ng·mL–1 for CoMOF-2. Furthermore, the developed sensors were employed to quantify 3-NT in real serum samples, with satisfactory results. In addition, the possible sensing mechanisms of CoMOFs toward the 3-NT biomarker were also discussed from photoinduced electron transfer and spectral overlaps. This work demonstrated the excellent potential of MOF-based sensors for biomarker detection in serum and provided an outlook to design MOF-based sensors with the help of artificial intelligence and machine learning.
2023-41
Platform for the Immobilizing of Ultrasmall Pd Clusters for Carbonylation: In Situ Self-Templating Fabrication of ZIF-8 on ZnO
Wei Yang, Fangchao Wang, He Wang, Ding Ding, Shaohua Jiang*, Guoying Zhang*
Small 2023, 2306794. https://doi.org/10.1002/smll.202306794 (IF:15.153/1Q/TOP)
Abstract: Incorporating metal clusters into the confined cavities of metal−organic frameworks (MOFs) to form MOF-supported catalysts has attracted considerable research interest with regard to carbonylation reactions. Herein, a self-templating method is used to prepare the zinc oxide (ZnO)-supported core–shell catalyst ZnO@Pd/ZIF-8. This facile strategy controls the growth of metal sources on the ZIF-8 shell layer and avoids the metal diffusion or aggregation problems of the conventional synthesis method. The characteristics of the catalysts show that the palladium (Pd) clusters are highly dispersed with an average particle size of ≈1.2 nm, making them excellent candidates as a catalyst for carbonylation under mild conditions. The optimal catalyst (1.25-ZnO@Pd/ZIF-8) exhibits excellent activity in synthesizing α, β-alkynyl ketones under 1 atm of carbon monooxide (CO), and the conversion rate of 1, 3-diphenylprop-2-yn-1-one is 3.09 and 3.87 times more than those of Pd/ZIF-8 and Pd2+, respectively, for the first 2 h. Moreover, the 1.25-ZnO@Pd/ZIF-8 is recyclable, showing negligible metal leaching, and, under the conditions used in this investigation, can be reused at least five times without considerable loss in its catalytic efficiency. This protocol can also be applied with other nucleophile reagents to synthesize esters, amides, and acid products.
2023-40
Inspired by Wood: Thick Electrodes for Supercapacitors
Feng Wang, Jiyoung Lee, Lian Chen, Guoying Zhang*, Shuijian He, Jingquan Han, Jaewan Ahn, Jun Young Cheong, Shaohua Jiang*, and Il-Doo Kim*
ACS Nano 2023, 17, 10, 8866-8898. doi/10.1021/acsnano.3c01241 (IF:18.027/1Q/TOP)
Abstract: The emergence and development of thick electrodes provide an efficient way for the high-energy-density supercapacitor design. Wood is a kind of biomass material with porous hierarchical structure, which has the characteristics of a straight channel, uniform pore structure, good mechanical strength, and easy processing. The wood-inspired low-tortuosity and vertically aligned channel architecture are highly suitable for the construction of thick electrochemical supcapacitor electrodes with high energy densities. This review summarizes the design concepts and processing parameters of thick electrode supercapacitors inspired by natural woods, including wood-based pore structural design regulation, electric double layer capacitances (EDLCs)/pseudocapacitance construction, and electrical conductivity optimization. In addition, the optimization strategies for preparing thick electrodes with wood-like structures (e.g., 3D printing, freeze-drying, and aligned-low tortuosity channels) are also discussed in detail. Further, this review presents current challenges and future trends in the design of thick electrodes for supercapacitors with wood-inspired pore structures. As a guideline, the brilliant blueprint optimization will promote sustainable development of wood-inspired structure design for thick electrodes and broaden the application scopes.
媒体报道相关链接：http://www.polymer.cn/sci/kjxw21471.html
2023-39
Qianqian Liang , Chunyan Zhang, Fangchao Wang, Zhong Luo, Wei Yang, Guohui Zhang , Ding Ding, Guoying Zhang*
SCIENCE CHINA Chemistry, 2023, 2391. DoI.org/10.1007/s11426-022-1576-5 (2023) (IF: 10.152/Q1/TOP)
Abstract: Noble metal catalysts are generally expensive, and thus, abundant 3d metals recently received significant attention as catalysts in catalytic hydrogenation. Mn catalysts are widely applied in transfer hydrogenations, but the reported catalyst loadings remain up to three orders of magnitude higher than noble metals. Thus, catalyst consumption should be overcome before 3d metal catalytic systems may be utilized practically in industry. Here, a catalytic system based on novel, scalable triazole N5-ligands coordinated to Mn is presented for use in transfer hydrogenations. Based on pre-activation via dehydrohalogenation, an unprecedented, efficient catalytic system operating via synergistic H-bond auxiliary activation was established. The Mn catalysts are practical at metal concentrations 0.0001 mol%, generating alcohol with TON up to 857 200, thus approaching loadings more conventionally observed in precious-metal-based systems. Notably, using this protocol, several pharmaceuticals may be easily synthesized in one pot.
2023-38
Morph-genetic bamboo-reinforced hydrogel complex for bio-mimetic actuator.
L. Chen, K. Zhang, J. Ahn, F. Wang , Y. Sun, J. Lee, J. Y. Cheong, C. Ma, H. Zhao, G. Duan, G. Zhang,* X. Yang,* , I.-D. Kim,* S. Jiang,*
Chemical Engineering Journal, 2023, 463, 142391. DoI: doi.org/10.1016/j.cej.2023.142391(2023) (IF: 16.744/Q1)
Abstract
Stimuli-responsive hydrogels are most promising for the fabrication of autonomous bio-mimetic soft actuators. However, their weak actuation forces and isotropic volume change hinder their practical utilization as versatile actuators, owing to their fragility. Herein, we used the morph-genetic method to fabricate anisotropic bamboo/poly(N-isopropylacrylamide) hydrogel (ABH) complex for use as soft actuator. First of all, the bamboo fiber structure provides an anisotropic framework for the ABH actuator to achieve precise deformational programmability. Secondly, benefiting from the ultra-high directional strength (110 MPa) of bamboo, ABH actuator exhibits sufficiently robust mechanical property, which generates a powerful actuating force. Lastly, owing to the regulation of bamboo sheet and PNIPAM hydrogel, the ABH actuator not only achieves ultra-fast response speed (825°/s of the bending speed), but also has excellent synergetic performance. We demonstrate several bio-mimetic actuating devices based on ABH actuator, inspired by the intricate motions of natural organisms, to highlight how the specific materials properties and their synergy can be systematically exploited for the rational design of soft actuators. Henceforth, it is anticipated that the development of hydrogel actuators could continue to benefit from the use of various naturally-anisotropic materials, such as shape-memory polymers or liquid crystals, for the preparation of further advanced hydrogel actuators by the morph-genetic method.
2022-37
Formamidation of a wide range of substituted and functionalized amines with CO and a base.
Zhang, C., Zhang, Y., Liang, Q., Zhang, G., Yang, W., Li, N., Qin, G* and Zhang, G.*
Org. Chem. Front., 2022,9, 6142-6148. DoI: 10.1039/D2QO01312F (2022). (IF: 5.456/Q1)
Abstract: Current methods for preparing formamides are limited by the narrow substrate scope and requirement for harsh reaction conditions. A base-mediated formamidation of amines with CO (<2 bar) under mild conditions was developed, which enabled the synthesis of a wide range of formamides in 61% to 98% yields under transition-metal-free conditions. This provides a useful strategy for generating gram amounts of various aromatic and aliphatic amides.
2022-36
Nickel(Ⅰ)-catalyzed (de)hydrogenative coupling of amines and alkyl heteroarenes with alcohols.
Chunyan Zhang, Qianqian Liang, Wei Yang, Guohui Zhang, Maolin Hu* and Guoying Zhang*
Green Chem., 2022,24, 7368-7375. DoI: 10.1039/D2GC02206K (2022).
Abstract: A novel nickel(I) complex (di(2,2′-(1-phenyl-1H-1,2,4-triazole-3,5-diyl)dipyridine))(dibromine) nickel(I)bromide ([Ni-N4]Br) exhibited extremely high efficiency toward the (de)hydrogenative alkylation of amines and alkyl heteroarenes by alcohols. The catalytic performance can be attributed to the functionalized nitrogen ligand, which adopts a cationic coordination mode and the facile dissociation of coordinated water. This sustainable transformation is applicable to various alcohols, featuring good functional group tolerance with high selectivity under solvent free conditions. The synthetic strategy provides a green and efficient method for the construction of functionalized amines and unsaturated N-heteroaromatic derivatives.
2022-35
One Pot Synthesis of 1,2-Disubstituted Ethanones by Base-Mediated Reductive Homocoupling of Aldehydes.
Guohui Zhang, Qianqian Liang, Wei Yang, Shaohua Jiang, Zhiping Wang,* Chunyan Zhang,* Guoying Zhang*
Advanced Synthesis & Catalysis. 2022, 364, 2951-2956. DoI: org/10.1002/adsc.202200586 (2022).
Abstract: Reductive homocoupling transformations mediated by bases and TMSCN have been used as a strategy for synthesis of 1,2-disubstituted ethanones. This protocol provides a method for synthesizing functionalized ethanones from aldehydes in one pot without transition metals.
2021-34
Palladium-Catalyzed Allyl–Allyl Reductive Coupling of Allylamines or Allylic Alcohols with H2 as Sole Reductant
Xibing Zhou, Guoying Zhang, Renbin Huang, and Hanmin Huang*
Organic Letters 2021, 23, 2, 365-369
Abstract: Catalytic carbon–carbon bond formation building on reductive coupling is a powerful method for the preparation of organic compounds. The identification of environmentally benign reductants is key for establishing an efficient reductive coupling reaction. Herein an efficient strategy enabling H2 as the sole reductant for the palladium-catalyzed allyl–allyl reductive coupling reaction is described. A wide range of allylamines and allylic alcohols as well as allylic ethers proceed smoothly to deliver the C–C coupling products under 1 atm of H2. Kinetic studies suggested that the dinuclear palladium species was involved in the catalytic cycle.
2021-33
Synthesis of 1,3-diketones from esters via liberation of hydrogen.
Guoying Zhang, Torsten Irrgang, Martin Schlagbauer, and Rhett Kempe*
Chem. Catalysis. 2022, 1, 681-690. DoI: 10.1016/j.checat.2021.05.007 (2021).
Abstract: Catalytic reactions that convert green or sustainable starting mate-rials into important classes of chemical compounds, generate hydrogen, and are mediated by Earth-abundant element catalysts are highly desirable. Here, we report on a catalytic dehydrogenative rearrangement of esters into 1,3-diketones. Esters are green or sustainable and inexpensive starting materials that are available in great diversity, and 1,3-diketones are highly attractive building blocks for organic synthesis. The concerted interaction of a base acid catalyst and a dehydrogenation catalyst mediates our reaction. The dehydrogenation catalyst is based on manganese, and the hydrogen formed can be liberated and is the only by-product formed.
Chem Catal.：Mn-KOᵗBu协同催化酯脱氢重排制备1,3-二酮 https://www.x-mol.com/news/683421
2020-32
A practical base mediated synthesis of 1,2,4-triazoles enabled by a deamination annulation strategy.
Chunyan Zhang,* Zuyu Liang, Xiaofei Jia, Maorong Wang, Guoying Zhang,* Mao-Lin Hu*
Chem. Commun., 2020,56, 14215-14218. Doi:10.1039/D0CC05828A (2020).
Abstract: A practical and efficient base mediated synthesis of free 3-aminoindazoles has been developed from the reaction of nitriles with hydrazines, which successfully overcomes the difficulty of using aromatic hydrazines as substrates and allows for the synthesis of a wide range of N-aryl substituted free 3-aminoindazoles in moderate to excellent yields under mild conditions in one-pot. This finding provides a rapid and useful strategy for the synthesis of various functionalized 3-aminoindazole derivatives.
2020-31
Camellia pollen-derived carbon with controllable N content for high performance supercapacitor by ammonium chloride activation and dual-N-doping.
Lihua Cao, Huiling Li, Dr. Zhaoxiu Xu, Ruirui Gao, Prof. Suqing Wang, Prof. Guoying Zhang, Prof. Shaohua Jiang,* Dr. Wenhui Xu, Prof. Haoqing Hou*
ChemNanoMat 2021,7, 34-43. Doi:10.1002/cnma.202000531 (2020).
Abstract: Biomass-derived carbon materials are an amazing electrode material for supercapacitor, owing to their abundant, porous structure and composition. Herein, a controllable N content carbon material with hierarchical porous structure was fabricated via an integrated carbonization, activation and nitrogen-doping process. N-rich camellia pollen is used as carbon precursor, while NH4Cl is employed as both activation agent and dopant. The optimal N-doped carbon with higher N content (3.82 at%), suitable pore size distribution and larger specific surface area (810 m2 g−1), provides abundant ion transport channels and exposes more accessible active sites. Thus, a high specific capacitance of 280 F g−1 (1 A g−1) in 6 M KOH (three-electrode system) can be obtained with making full use of N−HPC-1. Moreover, the assembled symmetrical supercapacitor delivers high energy densities both in 6 M KOH (13.3 Wh kg−1) and 1 M Na2SO4 (20 Wh kg−1) that can be used for LED lighting. More than that, it is also demonstrates excellent cycle stability in 6 M KOH (85.4% after 20000 cycles at 20 A g−1). In view of the above-mentioned merits, this N-doped hierarchical porous carbon is anticipated to be a promising material for application in supercapacitors and other fields.
2020-30
A flame-retardant and transparent wood/polyimide composite with excellent mechanical strength
Lian Chen, Zhiwen Xu, Feng Wang, Gaigai Duan, Wenhui Xu, Guoying Zhang, Haoqi Yang,*, Jinbiao Liu, Shaohua Jiang*
Composites Communications 2020, 20, 100355. (IF:8.0/1Q/TOP)
Abstract: Transparent wood (TW), as a promising structural material, has attracted considerable attention owing to the high transmittance, excellent toughness, outstanding modulus and mechanical strength. Despite the encouraging achievements on TW materials have been made, their widespread applications are still restricted by the intrinsic flammability. Herein, in this work, a flame-retardant TW/polyimide (FRTW/PI) composite has been prepared by successfully impregnating polyimide into delignified porous wood template. As expected, the FRTW/PI composite maintains good self-extinguishing properties after leaving the fire source within 2 s. Additionally, the FRTW/PI composite exhibits an enhanced mechanical strength of 169 MPa, which is 42 times higher than that of natural wood (NW) and much higher than other previously reported values. This work put forwards an effective approach for the fabrication of FRTW/PI composite and holds a great promise as colored glass for future buildings.
2020-29
N-doped honeycomb-like porous carbon towards high-performance supercapacitor.
Feng Wang, Lian Chen, Huiling Li, Gaigai Duan, Shuijian He, Lin Zhang, Guoying Zhang, Zhengping Zhou, Shaohua Jiang*
Chinese Chemical Letters 2020, 31, 1986-1990. Doi:10.1016/j.cclet.2020.02.020 (2020). (IF: 8.455)
Abstract: Biomass-derived porous carbon with developed pore structure is critical to achieving high performance electrode materials. In this work, we report a grape-based honeycomb-like porous carbon (GHPC) prepared by KOH activation and carbonization, followed by N-doping (NGHPC). The obtained NGHPC exhibits a unique honeycomb-like structure with hierarchically interconnected micro/mesopores, and high specific surface area of 1268 m2/g. As a supercapacitor electrode, the NGPHC electrode exhibits a remarkable specific capacitance of 275 F/g at 0.5 A/g in a three-electrode cell. Moreover, the NGHPC//NGHPC symmetric supercapacitor displays a high energy density of 12.6 Wh/kg, and excellent cycling stability of approximately 95.2% capacitance retention after 5000 cycles at 5 A/g. The excellent electrochemical performance of NGHPC is ascribed to its high specific surface area, honeycomb-like structure and high-content of pyrodinic-N (36.29%). It is believed that grape-based carbon materials show great potential as advanced electrode materials for supercapacitors.
2020-28
Base-Mediated Amination of Alcohols Using Amidines.
Chunyan Zhang, Zehua Li, Jianbin Chen, Shuo Qi, Yanchen Fang, Sheng Zhang, Chaoyu Ren, Fenghong Lu, Zuyu Liang, Shaohua Jiang, Xiaofei Jia, Shuangming Yu, and Guoying Zhang*
The Journal of Organic Chemistry 2020, 85, 12, 7728-7738. Doi:10.1021/acs.joc.0c00281 (2020).
Abstract: Novel and efficient base-mediated N-alkylation and amidation of amidines with alcohols have been developed, which can be carried out in one-pot reaction conditions, which allows for the synthesis of a wide range of N-alkyl amines and free amides in good to excellent yields with high atom economy. In contrast to borrowing hydrogen/hydrogen autotransfer or oxidative-type N-alkylation reactions, in which alcohols are activated by transition-metal-catalyzed or oxidative aerobic dehydrogenation, the use of amidines provides an effective surrogate of amines. This circumvents the inherent necessity in N-alkylation of an oxidant or a catalyst to be stabilized by ligands.
2020-27
Base-mediated cascade amidination/N-alkylation of amines by alcohols.
Chunyan Zhang,* Zuyu Liang, Fenghong Lu, Xiaofei Jia, Guoying Zhang* and Mao-Lin Hu*
Chem. Commun., 2020,56, 10489-10492. Doi:10.1039/d0cc04831c (2020).
Abstract: A base-mediated cascade amidination/N-alkylation reaction of amines by alcohols has been developed. For the first time, nitriles have been identified as an efficient and benign water acceptor reagent in N-alkylation. Notably, the procedure tolerates a series of functional groups, such as methoxyl, halo, vinyl and hetero groups, providing a convenient method to construct different substituted diamino compounds, 15N labeled amine and could be scaled up to 1 mol scale offering 138.7 g of the desired product in good yield in one-pot. Mechanistic studies provided strong evidence for the amidination of amines with nitriles facilitated by t-BuOK.
2020-26
Rapid access to 3-aminoindazoles from nitriles with hydrazines: a strategy to overcome the basicity barrier imparted by hydrazines.
Chunyan Zhang,* Haowen Zhao, Zehua Li, Zuyu Liang, Shuo Qi, Mingyu Cai, Sheng Zhang, Xiaofei Jia, Guoying Zhang* and Mao-Lin H*
Chem. Commun., 2020,56, 9521-9524. Doi:10.1039/d0cc03789c (2020).
Abstract: A practical and efficient base mediated synthesis of free 3-aminoindazoles has been developed from the reaction of nitriles with hydrazines, which successfully overcomes the difficulty of using aromatic hydrazines as substrates and allows for the synthesis of a wide range of N-aryl substituted free 3-aminoindazoles in moderate to excellent yields under mild conditions in one-pot. This finding provides a rapid and useful strategy for the synthesis of various functionalized 3-aminoindazole derivatives.
2020-25
Zhang, C. Y., Li, Z. H., Fang, Y. C., Jiang, S. H., Wang, M. R. & Zhang, G.*
MnO2 mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols.
Tetrahedron 76, 130968. Doi:10.1016/J.Tet.2020.130968 (2020).
2020-24
Scalable Electrochemical Transition-Metal-Free Dehydrogenative Cross-Coupling Amination Enabled Alkaloid Clausines Synthesis.
Pan Zhang, Baoying Li, Liwei Niu, Ling Wang, Guofeng Zhang, Xiaofei Jia, Guoying Zhang, Siyuan Liu, Li Ma, Wei Gao, Dawei Qin, Jianbin Chen*
Advanced Synthesis & Catalysis 362, 2342-2347. Doi:10.1002/adsc.202000228 (2020).
Abstract: A strategy for synthesis of azo-derived compounds by electrochemical oxidative ring-opening reactions of 2H-indazoles with alcohols is reported. The reactions are carried out under galvanostatic electrolysis conditions in an undivided cell without the use of transition metal catalysts. On the basis of cyclic voltammetry and control experiments, a plausible mechanism for this ring-opening reaction involving the radical pathway is proposed. Furthermore, various 2H-indazoles and alcohols are suitable in this system, giving the desired ortho-alkoxycarbonylated azobenzenes in 9–84% yields.
2020-23
有机聚合物负载铑催化剂在氢甲酰化反应中的应用研究进展.
宗玲博, 陈., 任新意, 张国营, 贾肖飞.*
有机化学 40, 2308-2321. Doi:10.6023/cjoc202003006 (2020).
摘要：氢甲酰化反应是工业上最重要的均相反应之一.该反应被广泛应用于醛的生产，生产的醛还可以进一步转为具有高附加值的醇、酸等衍生物.与均相反应相比，多相催化在催化剂循环、产物和催化剂分离等方面具有优势.近年来，有机聚合物负载铑催化剂在非均相的甲酰化反应中表现出优秀的催化活性、高的选择性和好的循环性等优点，因而受到广泛关注.总结了有机聚合物负载催化剂在氢甲酰化反应中应用研究进展，主要介绍了催化剂的合成、材料特点和应用，最后对发展前景进行了展望.
Abstract: Hydroformylation is considered one of the most important homogenously catalyzed processes in dustry. Hydroformylation has been widely used in the production of aldehydes, and aldehydes can also be further converted into high value-added alcohols, acids and other derivatives. Compared with the homogeneous reaction, the heterogeneous catalysts present significant advantages in terms of recyclability, separation of catalysts and products and so on. In recent years, organic polymer-supported rhodium catalysts have shown excellent catalytic activity, high selectivity, and good recycleability in heterogeneous hydroformylation, and have attracted widespread attention. The research progress of the application of organic polymer supported catalysts in hydroformylation is summarized, including synthesis, material characteristics and application of supported catalysts. Finally, the prospect of the reaction is discussed.
2019-22
Porous organic polymer supported rhodium as a heterogeneous catalyst for hydroformylation of alkynes to alpha,beta-unsaturated aldehydes.
Zuyu Liang, Jianbin Chen, Xin Chen, Kai Zhang, Jinhe Lv, Haowen Zhao, Guoying Zhang, Congxia Xie, Lingbo Zong and Xiaofei Jia
Chem. Commun., 2019,55, 13721-13724. Doi:10.1039/c9cc06834a (2019).
Abstract: A new porous organic polymer supported rhodium catalyst (Rh/POL-BINAPa&PPh3) has been developed for the hydroformylation of various alkynes to afford the corresponding α,β-unsaturated aldehydes with high chem- and stereoselectivity, excellent catalytic activity and good reusability (10 cycles). The heterogeneous catalyst exhibited more catalytic activity than the comparable homogeneous Rh/BINAPa/PPh3 system.
2018-21
Palladium-catalyzed regiodivergent hydroaminocarbonylation of alkenes to primary amides with ammonium chloride.
Bao Gao, Guoying Zhang, Xibing Zhou and Hanmin Huang.*
Chem. Sci., 2018,9, 380-386. Doi:10.1039/c7sc04054g (2018).
Abstract: Palladium-catalyzed hydroaminocarbonylation of alkenes for the synthesis of primary amides has long been an elusive aim. Here, we report an efficient catalytic system which enables inexpensive NH4Cl to be utilized as a practical alternative to gaseous ammonia for the palladium-catalyzed alkene-hydroaminocarbonylation reaction. Through appropriate choice of the palladium precursors and ligands, either branched or linear primary amides can be obtained in good yields with good to excellent regioselectivities. Primary mechanistic studies were conducted and disclosed that electrophilic acylpalladium species were capable of capturing the NH2-moiety from ammonium salts to form amides in the presence of CO with NMP as a base.
2018-20
Base-catalyzed selective esterification of alcohols with unactivated esters.
Chunyan Zhang,* Guoying Zhang,* Shizhong Luo, Chunfu Wang and Huiping Li
Org. Biomol. Chem., 2018,16, 8467-8471. Doi:10.1039/c8ob02411a (2018).
Abstract: A practical and efficient base-catalyzed esterification has been developed for the facile synthesis of a broad range of esters from simple alcohols with unactivated tert-butyl esters. This protocol could be conducted at mild conditions, providing esters in high to excellent yields with good functional tolerance. Mechanistic studies provided evidence of an exchange of the tert-butyl alkoxide metal with the alcohol, producing a new alkoxide to participate in the transesterification reaction.
2018-19
Manganese-Catalyzed Dehydrogenative Alkylation or alpha-Olefination of Alkyl-Substituted N-Heteroarenes with Alcohols.
Guoying Zhang, Torsten Irrgang, Thomas Dietel, Fabian Kallmeier, Rhett Kempe*
Angewandte Chemie International Edition, 2018, 57, 9131-9135. Doi:10.1002/anie.201801573 (2018).
Abstract: Catalysis with earth-abundant transition metals is an option to help save our rare noble-metal resources and is especially interesting when novel reactivity or selectivity patterns are observed. We report here on a novel reaction, namely the dehydrogenative alkylation or α-olefination of alkyl-substituted N-heteroarenes with alcohols. Manganese complexes developed in our laboratory catalyze the reaction with high efficiency whereas iron and cobalt complexes stabilized by the same ligands are essentially inactive. Hydrogen is liberated during the reaction, and bromine and iodine functional groups as well as olefins are tolerated. A variety of alkyl-substituted N-heteroarenes can be functionalized, and benzylic and aliphatic alcohols undergo the reaction.
2018-18
Palladium-Catalyzed Hydrocarbonylative C–N Coupling of Alkenes with Amides.
Xibing Zhou, Guoying Zhang, Bao Gao, and Hanmin Huang*
Organic Letters 20, 2208-2212. Doi:10.1021/acs.orglett.8b00538 (2018).
Abstract: An efficient palladium-catalyzed hydrocarbonylative C–N coupling of alkenes with amides has been developed. The reaction was performed via hydrocarbonylation of alkenes, followed by acyl metathesis with amides. Both intermolecular and intramolecular reactions proceed smoothly to give either branched or linear amides in high turnover number (3500) with NH4Cl or NMP·HCl as a proton source under the palladium catalysis. This reaction offers a catalytic convenient approach to deuterated amides when inexpensive NMP·DCl served as a deuterium source.
2017-17
Ni-Catalyzed Dimerization and Arylation of Diarylacetylenes with Arylboronic Acids.
Yang Liu, Guoying Zhang, and Hanmin Huang*
Organic Letters 2017, 19, 24, 6674-6677. Doi:10.1021/acs.orglett.7b03398 (2017).
Abstract: A new, facile, and efficient protocol for the synthesis of polysubstituted conjugated 1,3-dienes through Ni-catalyzed tandem dimerization/cross-coupling reaction of diarylacetylenes and arylboronic acids in the presence of a catalytic amount of B2pin2 has been developed. A series of arynes and arylboronic acids with different substituents participated well in this catalytic system, affording a variety of useful conjugated 1,3-dienes.
2016-16
Palladium-Catalyzed Direct Amination of Allylic Alcohols at Room Temperature.
Gao, B. Z Li, L. Zhang, G. & Huang, H.*
Organic Syntheses 93, 341-351. Doi:10.15227/orgsyn.093.0341 (2016).
2016-15
Palladium-catalyzed hydroaminocarbonylation of alkenes with amines promoted by weak acid.
Guoying Zhang, Xiaolei Ji, Hui Yu, Lei Yang, Peng Jiao,* Hanmin Huang*
Tetrahedron Letters 57, 383-386. Doi:10.1016/j.tetlet.2015.12.031 (2016).
Abstract: The weak acid has been identified as an efficient basicity-mask to overcome the basicity barrier imparted by aliphatic amines in the Pd-catalyzed hydroaminocarbonylation, which enables both aromatic and aliphatic amines to be applicable in the palladium-catalyzed hydroaminocarbonylation reaction. Notably, by using this protocol, the marketed herbicide of Propanil and drug of Fentanyl could be easily obtained in a one-pot manner.
2015-14
Palladium-Catalyzed Dearomative Cyclocarbonylation by C-N Bond Activation.
Hui Yu, Guoying Zhang(共一作者), Hanmin Huang*
Angewandte Chemie International Edition, 2015, 54, 10912-10916. Doi:10.1002/anie.201504805 (2015).
Abstract: A fundamentally novel approach to bioactive quinolizinones is based on the palladium-catalyzed intramolecular cyclocarbonylation of allylamines. [Pd(Xantphos)I2], which features a very large bite angle, has been found to facilitate the rapid carbonylation of azaarene-substituted allylamines into bioactive quinolizinones in good to excellent yields. This transformation represents the first dearomative carbonylation and is proposed to proceed by palladium-catalyzed CN bond activation, dearomatization, CO insertion, and a Heck reaction.
2015-13
Palladium-catalyzed hydroaminocarbonylation of alkenes with amines: a strategy to overcome the basicity barrier imparted by aliphatic amines.
Guoying Zhang, Bao Gao, Hanmin Huang*
Angewandte Chemie International Edition, 2015, 54, 7657-7661. Doi:10.1002/anie.201502405 (2015).
Abstract: The basicity of aliphatic amines precludes their use in the palladium-catalyzed hydroaminocarbonylation. This issue was overcome by using aminals as surrogates of aliphatic amines. A cooperative catalytic system was discovered to operate by the synergistic combination of palladium, paraformaldehyde, and acid for promotion of the hydroaminocarbonylation of alkenes with both aromatic and aliphatic amines.
2015-12
Diboron as a reductant for nickel-catalyzed reductive coupling: rational design and mechanistic studies.
Guoying Zhang, Yinjun Xie, Zhengkun Wang, Yang Liu and Hanmin Huang*
Chem. Commun., 2015,51, 1850-1853. Doi:10.1039/c4cc08703h (2015).
Abstract: Diboron (B2pin2) has been identified as an efficient and environmentally benign reducing reagent for reductive coupling reactions for the first time, which enables the nickel-catalyzed reductive tetramerization of alkynes to be performed with high efficiency. Mechanistic and kinetic studies indicate that the facile reductive elimination to form the B–B bond from the dinuclear Ni–Ni complexes is responsible for the high efficiency. The activation enthalpy (ΔH‡ = 56.5 kJ mol−1), entropy (ΔS‡ = −128 J mol−1 K−1) and the substituent effect (ρ = 1.43) on this reaction were obtained.
2014-11
Rh-catalyzed sequential oxidative C-H and N-N bond activation: conversion of azines into isoquinolines with air at room temperature.
Wenjia Han, Guoying Zhang, Guangxing Li*, and Hanmin Huang*
Organic Letters 2014, 16, 13, 3532-3535. Doi:10.1021/ol501483k (2014).
Abstract: A rhodium-catalyzed sequential oxidative C–H annulation reaction between ketazines and internal alkynes has been developed via C–H and N–N bond activation with air as an external oxidant, which led to an efficient approach toward isoquinolines with high atom efficiency at rt. Utilizing the distinctive reactivity of this catalysis, both N-atoms of the azines could be efficiently incorporated to the desired isoquinolines under very robust and mild reaction conditions.
2014-10
An Efficient Rhodium/Oxygen Catalytic System for Oxidative Heck Reaction of Indoles and AlkenesviaCH Functionalization.
Lei Yang, Guoying Zhang, Hanmin Huang*
Advanced Synthesis & Catalysis 356, 1509-1515. Doi:10.1002/adsc.201301107 (2014).
Abstract: A rhodium(III)-catalyzed direct selective C-2 alkenylation reaction of indoles with alkenes has been developed with molecular oxygen as the sole oxidant. The rhodium/oxygen catalytic system is applicable to a broad range of indoles and alkenes, which provides a novel access to various C-2 alkenylated indoles and pyrroles.
2014-9
Palladium-catalyzed carbonylation of allylamines via C–N bond activation leading to β,γ-unsaturated amides.
Hui Yu, Guoying Zhang, Zong-Jian Liu and Hanmin Huang*
RSC Adv. 4, 64235-64237. Doi:10.1039/c4ra13939a (2014).
Abstract: Pd(Xantphos)Cl2 has been identified as an efficient catalyst for the direct carbonylation of allylamines via C–N bond activation. The reaction proceeds smoothly and provides β,γ-unsaturated amides in good to excellent yields under relatively mild conditions.
2014-8
Rh-Catalyzed oxidative C–H activation/annulation: converting anilines to indoles using molecular oxygen as the sole oxidant.
Guoying Zhang, Hui Yu, Guiping Qin and Hanmin Huang*
Chem. Commun., 2014,50, 4331-4334. Doi:10.1039/C3CC49751H (2014).
Abstract: A practical and efficient Rh(III)-catalyzed aerobic C–H activation has been developed for the facile synthesis of a broad range of indoles from simple anilines and alkynes. The protocol could be conducted under mild conditions and used environmentally friendly oxygen as the sole clear oxidant.
2013-7
Catalytic cross deoxygenative and dehydrogenative coupling of aldehydes and alkenes: a redox-neutral process to produce skipped dienes.
Bo Qian, Guoying Zhang, Yongzheng Ding and Hanmin Huang*
Chem. Commun., 2013,49, 9839-9841. Doi:10.1039/C3CC45428B (2013).
Abstract: A novel catalytic cross deoxygenative and dehydrogenative coupling reaction of aldehydes and alkenes was established via a cooperative catalysis approach. This transformation provided an efficient and atom-economic protocol for the synthesis of 1,4-skipped dienes from aldehydes and simple alkenes under oxidant-free reaction conditions.
2013-6
An efficient Rh/O2 catalytic system for oxidative C-H activation/annulation: evidence for Rh(I) to Rh(III) oxidation by molecular oxygen.
Guoying Zhang, Lei Yang, Yanyu Wang, Yinjun Xie, and Hanmin Huang*
Journal of the American Chemical Society 2013, 135, 24, 8850-8853. Doi:10.1021/ja404414q (2013).
Abstract: A novel and efficient Rh/O2 catalytic system has been developed and shown to catalyze highly efficient oxidative C–H activation/annulation reactions, producing a broad range of isoquinolinium salts with high turnover numbers (up to 740). Mechanistic studies provided strong evidence of facile oxidation of Rh(I) to Rh(III) by molecular oxygen facilitated by acid.
2013-5
Palladium-catalyzed cyanation of aryl halides with CuSCN.
Guo-Ying Zhang, Jin-Tao Yu, Mao-Lin Hu, and Jiang Cheng*
The Journal of Organic Chemistry 2013, 78, 6, 2710-2714. Doi:10.1021/jo3025829 (2013).
Abstract: A palladium-catalyzed cyanation of aryl halides and borons has been developed by employing cuprous thiocyanate as a safe cyanide source. This protocol avoids the use of a highly toxic cyanide source, providing aromatic nitriles in moderate to good yields with good functional tolerance.
2011-4
Copper-Mediated Cyanation of Aryl Halide with the Combined Cyanide Source.
Guoying Zhang, Xinyi Ren, Jianbin Chen, Maolin Hu,* and Jiang Cheng*
Organic Letters 2011, 13, 19, 5004-5007. Doi:10.1021/ol201713b (2011).
Abstract: A simple copper-mediated cyanation of aryl halide with the combination of ammonium bicarbonate and N,N-dimethylformamide as a cyanide source is achieved, providing nitriles in moderate to good yields. This new approach represents an exceedingly practical and safe method for the synthesis of aryl nitriles.
2011-3
Copper(I)-Mediated Cyanation of Boronic Acids.
Guoying Zhang, Lingli Zhang, Maolin Hu, Jiang Cheng*
Advanced Synthesis & Catalysis 353, 291-294. Doi:10.1002/adsc.201000747 (2011).
Abstract: A simple cyanation reaction of boronic acids with cuprous cyanide is achieved, providing nitriles in moderate to good yields. In the presence of copper(I) iodide, trimethylsilyl cyanide is also a good cyanating reagent. The reaction can be conducted on a 10-mmol scale. Thus, this new approach represents an exceedingly practical method for the synthesis of nitriles.
2011-2
Palladium/NHC-catalyzed oxidative esterification of aldehydes with phenols.
Manli Zhang, Shouhui Zhang, Guoying Zhang, Fan Chen,* Jiang Cheng*
Tetrahedron Letters 52, 2480-2483. Doi:10.1016/j.tetlet.2011.03.017 (2011).
Abstract: A palladium-catalyzed oxidative esterification of aldehydes with phenols is described, using air as the clean oxidant. This reaction tolerates many functional groups, providing esters with yields ranging from moderate to excellent.
2010-1
Cu(OTf)(2)-mediated Chan-Lam reaction of carboxylic acids to access phenolic esters.
Lingli Zhang, Guoying Zhang, Manli Zhang, and Jiang Cheng*
The Journal of Organic Chemistry 2010, 75, 21, 7472-7474 . Doi:10.1021/jo101558s (2010).
Abstract: Cu(OTf)2-mediated Chan-Lam reaction of carboxylic acids with arylboronic acids is described. It represents a facile and practical methodology to access phenolic esters in moderate to good yields. The procedure tolerates a series of functional groups, such as methoxycarbonyl, acetoxy, free phenolic hydroxyl, vinyl, nitro, trifluoromethyl, methoxyl, bromo, chloro, iodo, and acetyl groups.
