TETRAHEDRON
·
2017
·
IF 2.651
Cuiling Wang,Jiaxu Yan,Mo Du,Joseph A. Burlison,Chi Li,Yanni Sun,Danqing Zhao,Jianli Liu
One step synthesis of the natural product indirubin by reductive coupling of isatin with KBH 4 is described and a possible mechanism for the reaction is proposed. Eleven indirubin derivatives were obtained easily from the corresponding substituted isatin.
研究领域:
有机化学
·
药物化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 8
·2129-2137
·
IF 9.405
Di Liu,Ping Yang,Hao Zhang,Minjie Liu,Wenfei Zhang,Dongmei Xu,Jun Gao
A non-noble heterogeneous catalyst – a Co, N and C composite encapsulated carbon nanotube grown in situ on the surface of activated carbon (Co–N–C/CNT@AC) – was fabricated via the pyrolysis–reduction process. Co–N–C/CNT@AC catalyzed the reductive coupling of structurally diverse nitroarenes and alcohols to imines and secondary amines under exogenous base- and solvent-free conditions. BET, TEM, SEM, XRD and XPS characterization showed that the exceptional catalytic property of Co–N–C/CNT@AC could be explained by its nanostructure, Co–N and basic N species. Our protocol had advantages of low cost, environment-friendliness, and good applicability. Furthermore, a reaction route of nitroarenes, amines and alcohols as the starting materials was proposed to improve the atom economy of the reductive coupling of nitroarenes with alcohols.
研究领域:
化学
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环境科学
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材料科学
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DOI
高影响因子
SYNTHESIS-STUTTGART
·
2013
·Vol. 45
·期 16
·2234-2240
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IF 2.5
Wenbin Lu,Zhuye Liang,Yuwei Zhang,Fan Wu,Qun Qian,Hegui Gong
Alkyl aryl ketones were prepared on a gram scale by the nickel-catalyzed reductive coupling of alkyl iodides with aroyl chlorides. When scaled up 30-fold, this reaction shows a comparable coupling efficiency to the previously reported reaction performed under small-scale conditions. The mild and convenient reaction conditions show excellent tolerance to a range of functional groups and provide the ketones in good to excellent yields.
研究领域:
有机化学
·
合成化学
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DOI
高影响因子
JACS Au
·
2024
·
IF 8.5
Xixi Liu,Liang Huang,Yurong He,Peng Zhou,Xuedan Song,Zehui Zhang
It remains challenging to construct C═N bonds due to their facile hydrogenation. Herein, a single Co atom catalyst was discovered to be active for the selective construction of C═N bonds toward the synthesis of imines and N-heterocycles via reductive coupling of nitroarenes with various alcohols, including inert aliphatic ones. DFT calculations and experimental data revealed that the transfer hydrogenation proceeded via the intramolecular hydride transfer and the transfer of H from the α-Csp3-H bond to the nitro group was the rate-determining step. The single Co atoms served as a bridge to transfer the electrons from the catalyst to the adsorbed alcohol molecules, resulting in the activation of the α-Csp3-H bond. Unlike metal nanoparticles, the C═N bonds in imine products can be reserved due to the large steric hindrance from substituents on C and N. DFT calculation also confirmed that transfer hydrogenation of the C═N bonds in imines is thermodynamically unfavored with a much higher energy barrier compared with the transfer hydrogenation of the –NO2 group (1.47 vs 1.15 eV).
研究领域:
化学
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催化反应
·
理论计算
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DOI
PubMed
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2024
·
IF 3.3
Jie Tang,Zhiyou Li,Qi Meng,Long Liu,Tianzeng Huang,Chunya Li,Qiang Li,Tieqiao Chen
A CuH-catalyzed reductive coupling of nitroarenes with phosphine oxides is developed, which produces a series of phosphamides in moderate to excellent yields with good functional group tolerance. Gram-scale synthesis and late-stage modification of nitro-aromatic functional molecule niclosamide are also successfully conducted. The mechanism study shows that the nitro group is transformed after being reduced to nitroso and a nucleophilic addition procedure is involved during the reaction.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
·
IF 9.965
Meichun Qin,Shiying Fan,Xinyong Li,Moses O. Tade,Shaomin Liu
Electroreductive C O coupling provides a prospective strategy for biomass derivative upgrading via reducing the number of oxygen-containing functional groups and increasing their molecular weight. However, exploring superior electrocatalysts with effective reactivity and high selectivity for target products are still a challenge. In this work, single atom Au surface derived NiMn 2 O 4 (SACs Au−NiMn 2 O 4 ) spinel synergetic composites were fabricated by a versatile adsorption-deposition method and applied in electroreductive self-coupling of benzaldehyde to dibenzyl ether . The SACs Au–NiMn 2 O 4 spinel synergetic composites enhanced electroreductive coupling of benzaldehyde, significantly improved the yield and selectivity of dibenzyl ether. Systematic characterizations and density functional theory calculation revealed that atomically dispersed Au occupied surface Ni 2+ vacancies, which played a dominated role in C O coupling of benzaldehyde. Detailed calculation results showed that benzaldehyde preferred to adsorb on Ni octa-hedral sites of NiMn 2 O 4 spinel synergetic structure, single atom Au surficial derivation over NiMn 2 O 4 further reduced the adsorption energy (E ads ) of benzaldehyde on SACs Au−NiMn 2 O 4 , thus the C O coupling of benzaldehyde to dibenzyl ether was promoted. Moreover, single atom Au surficial derivation lowered the energy barrier of rate-determining step, facilitated the formation of dibenzyl ether species. Our work also paves an avenue for rational design single atom materials using spinel as support.
研究领域:
化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Yuan Ziliang,Han Bo,Liu Bing,Sun Jie,Zhou Peng,Mu Rentao,Zhang Zehui
Reductive-coupling of nitro compounds and alcohols is a sustainable route for constructing C = N bonds in organonitrogen chemicals, yet challenging due to the inertness of α-C sp3 -H bond in alcohols and the vulnerability of C = N bonds towards hydrogenation. Here, we report the surprising catalytic activity of ultrafine alkaline-earth metal oxide MgO nanoclusters (0.9 ± 0.3 nm) that efficiently activate α-C sp3 -H bonds, facilitating the transfer hydrogenation and synthesis of value-added chemicals bearing C = N bonds with high to excellent yields (86–99%). Controlled experiments and characterizations showed the crucial role of oxygen vacancies (O v ) and local Mg environment (Mg-O bond) in MgO for substrate adsorption and activation via electronic interactions between substrate’s negatively charged oxygen atoms and O v sites in MgO nanoclusters. Theoretical calculation further confirmed that O v significantly lowered the energy barrier of the hydrogen atom transfer from α-C sp3 -H in ethanol to the nitro group in nitrobenzene (29.3 vs . 52.9 kcal/mol), which is the rate-determining step with the highest energy barrier in reductive-coupling reactions. Our method not only provides an efficient and sustainable pathway for synthesizing organonitrogen chemicals with C = N bonds but also inspires the exploration of main group element catalysts as alternatives to transition metal and noble metal catalysts for organic transformations.
研究领域:
催化化学
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材料科学
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有机合成
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysts
·
2023
·Vol. 13
·期 11
·1392
·
IF 3.9
Cuicui Wu,Kaifei Tian,Xuan Guo,Yunming Fang
The transition from fossil resources to renewable biomass for the production of valuable chemicals and biobased fuels is a crucial step towards carbon neutrality. Squalene, a valuable chemical extensively used in the energy, healthcare, and pharmaceutical fields, has traditionally been isolated from the liver oils of deep-sea sharks and plant seed oils. In this study, a biochemical synergistic conversion strategy was designed and realized to convert glucose to squalene by combining fermentation technology in yeast with reductive coupling treatment of dienes. First, glucose derived from hydrolysis of cellulose was used as a renewable resource, using genetically engineeredSaccharomyces cerevisiaeas the initial biocatalyst to produce β-farnesene with a titer of 27.6 g/L in a 2.5 L bioreactor. Subsequently, intermediate β-farnesene was successfully converted to squalene through the organopalladium-catalyzed reductive coupling reaction involving the formation of Pd(0)L2species. Under mild reaction conditions, impressive β-farnesene conversion (99%) and squalene selectivity (100%) were achieved over the Pd(acac)2catalyst at a temperature of 75 °C in an ethanol solvent after 5 h. This advancement may provide insights into broadening squalene production channels and accessing the complex skeletons of natural terpenoids from biorenewable carbon sources, offering practical significance and economic benefits.Keywords:squalene;β-farnesene;fermentation technology;reductive coupling of dienes;Saccharomyces cerevisiae
研究领域:
生物化学
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化学工程
·
微生物学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Ao Li,Jiran Li,Mengcheng Yin,Qizhen Zhang,Junhong Chen,Bozhong Pi,Minghao Bao,Changkun Song,Wei Shi,Chunpei Yu,Wenchao Zhang
The electrochemical synthesis of azo-bridged nitrogen-rich heterocyclic compounds has emerged as a promising strategy in the field of energetic materials due to its efficiency and controllability. Here, we present an innovative and environmentally benign electrocatalytic strategy employing cobalt phosphide (Co2P) nanowire arrays as cathodic catalysts for the safe and efficient synthesis of sodium 5,5′-azo-tetrazole under mild electrochemical conditions. Notably, the Co2P catalyst drives the reaction at a low potential of −0.4 V (vs Hg/HgO), which benefits from its unique needle-like morphology that optimizes electron transport pathways and active site distribution. By adjustment of the applied potential and reaction time, the yield of the reductive coupling can be effectively controlled. A detailed mechanistic pathway has been elucidated for the cathodic reductive coupling of sodium 5-nitrotetrazole mediated by Co2P electrodes. Electrochemical reduction at −0.6 V (vs Hg/HgO) and −0.8 V (vs Hg/HgO) yields a tunable mixture of sodium 5,5′-azo-tetrazole and its azoxy derivative, whereas exclusive generation of sodium 5,5′-azo-tetrazole is achieved at −1 V (vs Hg/HgO) through precise modulation of electron transfer kinetics. This voltage-gated synthesis paradigm establishes a novel electrochemical methodology for the programmable assembly of nitrogen-rich heterocyclic frameworks, offering unprecedented control over azo-linkage formation in energetic material design.
研究领域:
电化学
·
材料科学
·
纳米技术
·
有机合成
·
能源材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemSusChem
·
2023
·Vol. 16
·期 14
·e202300180
·
IF 8.4
Yinjian Zheng,Zhiyuan Wang,Peng Chen,Wenbiao Zhang,Qingsheng Gao
Graphical Roughness-dependence of Cu electrodes is for the first time identified in the electro-reductive coupling of nitro and carbonyl compounds. With increased roughness, the selectivity of nitrones decreases, while that of imines increases, thanks to the feasible control over the reduction of nitroarenes to hydroxylamines or amines on Cu I /Cu 0 interfaces. The electro-reductive coupling of nitro and carbonyl compounds enables a facile, environmentally friendly and energy benign transformation toward value-added nitrones or imines, but the selectivity is still challenging. Here, the surface roughness of Cu electrodes is introduced for the first time as the determinant to switch products from nitrones to imines owing to the controllable reduction of nitroarenes to hydroxylamines or amines on tailored Cu I /Cu 0 interfaces. The roughness-dependent selectivity, that is the decrease of nitrones and the increase of imines with enhanced roughness, is visible in the electro-reductive coupling of nitrobenzene and furfural. Thus, the high selectivity of nitrone (98 %) and imine (80 %) can be achieved on a surface smooth Cu foil and the one electrochemically roughened in the presence of I − , respectively. Such roughness-dependence of nitrone/imine selectivity on Cu electrodes is further verified in a wide substrate scope, highlighting the promise of surface/interfacial engineering for electrochemical synthesis.
研究领域:
电化学
·
有机合成
·
材料科学
·
表面科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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