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Direct C(sp3)-H functionalization with thiosulfonates via photoredox catalysis 通过光氧化催化实现硫代磺酸盐与 C(sp3)-H 的直接官能化
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.05.003
Linfeng Liu , Yujian Pang , Canliang Ma , Daiqing Zhou , Wenjie Zhang , Jin Huang , Jie Sun , Jiangkai Qiu , Yihuan Liu , Lei Shen , Zhenjiang Li , Kai Guo
While C(sp3)-S bonds exist in many biologically active compounds, the direct catalytic C(sp3)-H thiolation remains elusive. Herein, we report a convenient and green C(sp3)-H thiolation approach mediated by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst. A wide range of C(sp3)-H bond-containing etheric, allylic, alkyl, ketonic, amidic substrates and sulfonyl-based SOMOphiles participated in the reaction, producing thioethers with high efficiency. The present protocol features green characteristics, such as being free of harmful oxidants and additives; step-economic; redox-neutral; and amenable to scale-up assisted by continuous-flow technology.
虽然C(sp3)-S键存在于许多生物活性化合物中,但直接催化C(sp3)-H硫基化仍然难以捉摸。在此,我们报告了一种方便和绿色的C(sp3)-H硫代化方法,该方法使用十钨酸四丁基铵(TBADT)作为氢原子转移(HAT)光催化剂。多种含C(sp3)-H键的醚类、烯丙基、烷基、酮类、酰胺类底物和磺酰基亲som试剂参与了该反应,高效地生成了硫醚。本议定书具有绿色特点,如不含有害氧化剂和添加剂;step-economic;redox-neutral;并且可以在连续流技术的帮助下扩大规模。
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引用次数: 0
Synthesis of naphtho[1,2-b]furan-2-carbaldehydes and naphtho[2,1-b]furan-2-carbaldehydes via electrocatalytic 3,3-rearrangement/cyclization of propargylic aryl ethers under mild conditions 在温和条件下通过电催化丙炔基芳基醚的 3,3-重排/环化合成萘并[1,2-b]呋喃-2-羰基醛和萘并[2,1-b]呋喃-2-羰基醛
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.05.008
Kaili Cen , Mixia Ouyang , Guojun He , Zhouting Zeng , Qiaolin Wang , Xin Yu , Feng Zhao , Jinhui Cai
An electrocatalytic 3,3-rearrangement/cyclization approach has been developed for the transformation of aryl-substituted propargylic aryl ethers to naphtho[1,2-b]furan-2-carbaldehyde and naphtho[2,1-b]furan-2-carbaldehyde derivatives. The reaction proceeded efficiently under mild conditions in the absence of metal- and chemical-oxidant, yielding the desired products with good substrate scope and functional group tolerance via a radical pathway. Furthermore, the control experiment revealed that the phenylselenyl-substituted secondary alcohol might be intermediate, and the 18O labeling reaction indicated the oxygen source in the product possibly deriving from water. Significantly, further transformations of the product were conducted to showcase the utility of this electrosynthesis strategy.
采用电催化3,3重排/环化方法将芳基取代丙基芳醚转化为萘[1,2-b]呋喃-2-甲醛和萘[1,2-b]呋喃-2-甲醛衍生物。在没有金属和化学氧化剂的温和条件下,反应有效进行,通过自由基途径产生具有良好底物范围和官能团耐受性的所需产物。对照实验表明苯硒基取代仲醇可能是中间体,18O标记反应表明产物中的氧源可能来源于水。值得注意的是,该产品的进一步转化是为了展示这种电合成策略的实用性。
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引用次数: 0
Transaminase catalyzed asymmetric synthesis of active pharmaceutical ingredients 转氨酶催化的活性药物成分不对称合成
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.03.003
Yiman Cui, Yadong Gao, Licheng Yang
Chiral amine molecules constitute vital components of pharmaceutical ingredients. Recent years have witnessed a growing focus on the efficient synthesis of chiral amines. Transaminases, as catalysts, have emerged as green, efficient, and highly selective solutions for substrates containing ketones or aldehydes, demonstrating exceptional performance in the synthesis of active drug molecules and natural products. This review primarily centers on the application of transaminases in the synthesis of important drug molecules bearing chiral amine group on acyclic or cyclic backbones. We delve into specific examples, highlighting the catalytic prowess of the sole transaminase catalyst as well as the combination with other enzymes in cascade transformations. This review illustrates the primary challenges that transaminases face and provides practical solutions that have been developed in these contexts. These solutions encompass various strategies and techniques that enhance the applicability and efficiency of transaminase-catalyzed reactions. In closing, we offer an outlook on the future of transaminase applications, discussing potential developments and emerging areas where this green and selective catalysis may play a pivotal role.
手性胺分子是药物成分的重要组成部分。近年来,人们越来越关注手性胺的高效合成。转氨酶作为催化剂,已成为一种绿色、高效、高选择性的解决方案,可用于含有酮或醛的底物,在合成活性药物分子和天然产物方面表现出卓越的性能。本综述主要围绕转氨酶在合成无环或环状骨架上带有手性胺基团的重要药物分子中的应用展开。我们将深入探讨具体实例,重点介绍单一转氨酶催化剂的催化能力,以及在级联转化中与其他酶的组合。本综述说明了转氨酶面临的主要挑战,并提供了在这些情况下开发的实用解决方案。这些解决方案包括各种策略和技术,可提高转氨酶催化反应的适用性和效率。最后,我们对转氨酶应用的未来进行了展望,讨论了这种绿色、选择性催化作用可能发挥关键作用的潜在发展和新兴领域。
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引用次数: 0
Synthesis of bridged bicyclic thiazine-2-thione and thiazole-2-thiones through DBU-promoted regioselective annulation of quinone monoacetals under mild conditions 在温和条件下通过 DBU 促进醌单乙醛的区域选择性环化合成桥式双环噻嗪-2-硫酮和噻唑-2-硫酮
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2023.12.004
Hong Qin , Man Yang , Yuguang Li , Xiaobing Yang , Yujing Hu , Chengkou Liu , Wei He , Zheng Fang , Kai Guo
The first regioselective [4 ​+ ​2] annulation reactions of quinone monoacetals with isothiocyanates and Na2S have been accomplished. This convenient and novel protocol involves the synthesis of valuable bridged thiazine-2-thione and thiazole-2-thiones through DBU-promoted at room temperature. Mechanism study reveals the dearomative transformation possibly undergoes a radical cascade reaction on the structure of quinone monoacetals to an efficient synthesis of a broad range of thione-containing heterocyclic compounds with broad tolerance in moderate to excellent yields. Moreover, the reported procedure can be easily applied to a 1g scale.
首次完成了醌单缩醛与异硫氰酸酯和Na2S的区域选择性[4 + 2]环化反应。这一简便、新颖的方案涉及在室温下通过dbu促进合成有价的桥接噻唑-2-硫酮和噻唑-2-硫酮。机理研究表明,脱芳转化可能是在醌类单缩醛的结构上发生自由基级联反应,从而在中等到优异的产率下,高效地合成了多种具有广泛耐受性的含硫杂环化合物。此外,报告的过程可以很容易地应用于1g规模。
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引用次数: 0
Transformation of ambient CO2 in air into cyclic carbonates mediated by a phosphorus-nitrogen PN3-pincer iron complex 在磷-氮 PN3-钳铁复合物的介导下,将空气中的二氧化碳转化为环状碳酸盐
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.06.002
Li Yang , Priyanka Chakraborty , Pradip K. Das, Dongya Zhang, Kuo-Wei Huang
The atom-economical reaction of carbon dioxide (CO2) with epoxides possesses the potential to utilize captured CO₂ for synthesizing useful chemicals. Among a wide range of metal complexes employed for this transformation, iron (Fe) stands out because of its low cost, ready availability, and stability. In this work, a pyridine-based pincer PN³-Fe(II) complex was synthesized and used as an efficient catalyst for the CO₂ epoxide cycloaddition. More importantly, this complex enabled the direct capture of CO₂ in the atmosphere and conversion into cyclic carbonates in excellent yields.
二氧化碳(CO)与环氧化物的原子经济反应具有利用捕获的 CO₂ 合成有用化学品的潜力。在用于这种转化的各种金属复合物中,铁(Fe)因其低成本、随时可用性和稳定性而脱颖而出。在这项工作中,合成了一种基于吡啶的钳状 PN³-Fe(II) 复合物,并将其用作 CO₂ 环氧化物环加成反应的高效催化剂。更重要的是,这种配合物能够直接捕获大气中的 CO₂,并以极高的产率将其转化为环碳酸盐。
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引用次数: 0
Electrochemical selective deuterium labelling of N-heteroarenes N-teroarenes 的电化学选择性氘标记
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.06.003
Feiyu Qiu , Yi Chen , Peiqin Liao, Yuan Gao, Mian Guo, Heng Zhang, Aiwen Lei, Wu Li
Hydrogen-deuterium exchange (HIE) reaction is the most direct way to achieve the deuterium labeling as there is no need for extra pre-functionalization. Herein, we report an electrochemical selective deuterium labelling of N-heteroarenes using D2O. The formation of aromatic radicals has been directly identified by using the time-resolved electron paramagnetic resonance (EPR) technique under electrochemical conditions. Mechanistic studies revealed that the hydrogen/deuterium (H/D) exchange involved continuous redox of N-heteroarenes under paired electrolysis and the selectivity of deuteration was established by DFT calculations. This electrochemical synthesis method offers a promising avenue for deuterium incorporation at specific sites of aromatic compounds.
氢氘交换(HIE)反应是实现氘标记的最直接方法,因为它不需要额外的预官能化。在此,我们报告了一种利用 DO 对-heteroarenes 进行电化学选择性氘标记的方法。在电化学条件下,利用时间分辨电子顺磁共振(EPR)技术直接确定了芳香族自由基的形成。机理研究表明,在成对电解条件下,氢/氘(H/D)交换参与了-heteroarenes 的连续氧化还原,并通过 DFT 计算确定了氘化的选择性。这种电化学合成方法为在芳香族化合物的特定位点掺入氘提供了一种前景广阔的途径。
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引用次数: 0
Chiral bis(imidazoline) NCN pincer iridium(III)-catalyzed enantioselective alkynylation of trifluoropyruvates with terminal alkynes 手性双咪唑啉NCN钳形铱(III)催化三氟丙酮酸与末端炔的对映选择性炔化反应
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.08.006
Xiao-Qi Zhang , Hui-Jie Wang , Hui Jiang, Mao-Ping Song, Jun-Fang Gong
Readily prepared chiral bis(imidazoline) NCN pincer iridium(III) complexes have been developed as the new and highly stereoselective catalysts for the direct asymmetric addition of terminal alkynes to trifluoropyruvates. With a catalyst loading of 5 ​mol%, a variety of optically active α-trifluoromethylated tertiary propargylic alcohols were thus produced in good yields with high enantioselectivity (27 examples, 74%–96% ee). Both enantiomers of the catalysis products were obtained by using enantiomeric Ir(III) catalysts. In addition, gram scale synthesis of the product and its transformation to a potentially very useful 2H-1,2,3-triazole compound were accomplished. Control experiments suggested that the alkynylide Ir(III) intermediates were involved in the reactions.
手性双咪唑啉(NCN)钳形铱(III)配合物是三氟丙酮酸直接不对称加成的新型高立体选择性催化剂。在催化剂负载为5 mol%的情况下,多种具有光学活性的α-三氟甲基化叔丙醇的收率高,对映选择性高(27例,ee为74%-96%)。催化产物的两种对映体均采用对映体Ir(III)催化剂制备。此外,还完成了该产物的克级合成,并将其转化为潜在的非常有用的2h -1,2,3-三唑化合物。对照实验表明,炔烃类Ir(III)中间体参与了该反应。
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引用次数: 0
Iron-catalyzed carbonylative synthesis of tert-alkyl thioesters 铁催化羰基化合成叔烷基硫酯
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2024.11.005
Sufang Shao , Zhi-Peng Bao , Xiao-Feng Wu
In the context of transition metal-catalyzed carbonylation reactions, iron-catalyzed carbonylative transformation retains considerable value due to its high abundance, affordability, and diverse catalytic modes. Among the carbonylation reactions, non-activated bulky alkyl halides and highly reactive thiol compounds are considered to be particularly challenging substrates. In this study, we studied the synthesis of various steric alkyl thioesters through the reaction of non-activated steric alkyl iodides with S-aryl thioester as the aryl sulfur source catalyzed by iron salt. This reaction offers a convenient approach for the synthesis of hindered thioesters. Preliminary mechanistic studies indicated the involvement of radical intermediates.
在过渡金属催化羰基化反应的背景下,铁催化羰基化转化由于其丰度高、可负担性强和催化方式多样而保持了相当大的价值。在羰基化反应中,非活化的大体积烷基卤化物和高活性的硫醇化合物被认为是特别具有挑战性的底物。本研究以非活化的立体烷基碘化物为原料,在铁盐催化下以s -芳基硫酯为芳基硫源,合成了多种立体烷基硫酯。该反应为合成受阻硫酯提供了一种方便的方法。初步的机制研究表明自由基中间体的参与。
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引用次数: 0
Synthesis of nucleoside drugs for the treatment of HBV infection: An updated review 核苷类药物的合成治疗HBV感染:最新综述
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2025.06.001
Houzong Yao , Xianjing Zheng , Minjie Liu , Yuelun Xu , Ping Xu , Fen-Er Chen
Hepatitis B virus (HBV) is a significant global health concern, characterized by its potential to cause acute and chronic liver diseases. Despite the availability of effective vaccines and treatments, substantial gaps remain in the management of chronic infections, particularly in regions like China, where millions are affected. This review delves into the synthesis of clinical anti-HBV drugs, including lamivudine, adefovir, tenofovir, entecavir, and telbivudine, highlighting various synthetic strategies. By emphasizing efficient synthetic routes suitable for large-scale production, this review contributes valuable insights for enhancing treatment accessibility and improving patient outcomes in hepatitis B management.
乙型肝炎病毒(HBV)是一个重大的全球健康问题,其特点是可能导致急性和慢性肝脏疾病。尽管有有效的疫苗和治疗方法,但在慢性感染管理方面仍存在巨大差距,特别是在中国等有数百万人受到影响的地区。本文综述了拉米夫定、阿德福韦、替诺福韦、恩替卡韦和替比夫定等临床抗hbv药物的合成,重点介绍了各种合成策略。通过强调适合大规模生产的高效合成路线,本综述为提高乙型肝炎治疗可及性和改善患者预后提供了有价值的见解。
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引用次数: 0
Recent progress in selective liquid-phase hydrogenation of furfural on heterogeneous Ni-containing catalysts 多相含镍催化剂上糠醛选择性液相加氢研究进展
Pub Date : 2025-11-01 DOI: 10.1016/j.gresc.2025.04.001
Victoria S. Zhuravleva , Anastasiya A. Shesterkina , Anna A. Strekalova , Kseniia V. Vikanova , Alexander L. Kustov
Lignocellulose biomass, without any doubts, is one of the most promising, and, therefore, one of the most studied sources for the production of biofuels, valuable chemicals and “green” solvents. Furfural – a product of biomass catalytic conversion – is a well-known “platform” molecule, a starting material for the obtaining of a number of important chemical substances. Nowadays, the focus of the researchers is directed to the search for a suitable catalytic system for effective conversion of furfural. In this review, the recent advances in the development of Ni-based mono- and bimetallic catalytic systems for furfural hydrogenation as an alternative to the industrial toxic copper chromite catalyst were considered. Special attention was paid to the study of the catalytic properties of bimetallic Ni-Me (second metal) catalytic systems, as well as a detailed discussion of the mechanisms of furfural hydrogenation.
毫无疑问,木质纤维素生物质是最有前途的生物质之一,因此也是研究最多的生物燃料、有价值的化学品和“绿色”溶剂的生产来源之一。糠醛是生物质催化转化的产物,是一种众所周知的“平台”分子,是获得许多重要化学物质的起始材料。目前,研究人员的重点是寻找一种合适的催化体系来有效地转化糠醛。本文综述了近年来用于糠醛加氢的镍基单金属和双金属催化体系作为工业有毒铜铬铁矿催化剂的替代品的研究进展。重点研究了双金属Ni-Me(第二金属)催化体系的催化性能,并对糠醛加氢的机理进行了详细的讨论。
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引用次数: 0
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Green Synthesis and Catalysis
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