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N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crosssover for alkene dicarbofunctionalization(N-杂环腈催化光导自由基-极性交叉用于烯烃的二羧基官能化
Pub Date : 2024-03-18 DOI: 10.1016/j.gresc.2024.03.002
Youfeng Han, Beibei Zhang, Zhixiang Wang, Xiangyu Chen
The photoredox radical-polar crossover paradigm is a valuable tool for 1,2-difunctionalization of alkenes. However, the use of unactivated alkyl halides as radical precursors remains far less developed. Here, we report a photoreductive -heterocyclic nitrenium-catalyzed radical-polar crossover for the 1,2-dicarbofunctionalization of alkenes by using unactivated alkyl and aryl iodides. These reactions can be carried out under simple, transition-metal-free conditions with easily obtainable materials such as alkyl/aryl halides, alkenes, and aldehydes. The reactions exhibit a broad range of substrate compatibility and good tolerance towards functional groups. This approach offers a new tool to unlock the compatibility of carbon skeletons.
光氧化自由基-极性交叉范例是烯烃 1,2 双官能化的重要工具。然而,将未活化的烷基卤化物用作自由基前体的研究还远远不够。在此,我们报告了一种利用未活化的烷基和芳基碘化物进行光生化-杂环腈催化的自由基-极性交叉反应,用于烯烃的 1,2-二官能化。这些反应可以在简单、无过渡金属的条件下,利用烷基/芳基卤化物、烯烃和醛等容易获得的材料进行。这些反应具有广泛的底物兼容性和对官能团的良好耐受性。这种方法为揭示碳骨架的兼容性提供了一种新工具。
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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 : 2024-03-16 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
Unraveling chemical glycosylation: DFT insights into factors imparting stereoselectivity 揭开化学糖基化的神秘面纱:通过 DFT 深入了解赋予立体选择性的因素
Pub Date : 2024-03-15 DOI: 10.1016/j.gresc.2024.03.004
Aoxin Guo, Yuan Xu, Zhenhua Jia, Teck-Peng Loh, Xue-Wei Liu
Stereoselective chemical glycosylation reactions are pivotal for preparing manifold biologically and medically important compounds, while mechanisms of chemical glycosylation reactions remain obscure and largely speculative. Herein, we performed DFT calculations to delve into the multifaceted mechanistic details of glycosylation reactions, including the equilibria among reactive glycosyl triflate intermediates in solution, the stereoselectivity imparting protecting groups, solvent effects, base, and the anomeric effect. Our results provided theoretical corroborations to 2-OAc neighbouring group participation (NGP), the arming/disarming effect, the coordination theory of solvent effect on glycosylation stereochemistry, and the influence of solvent polarity on the reaction kinetics spanning the S1-S2 continuum. For the first time, the existence of putative contact-ion-pairs (CIP) of glycosyl oxocarbenium and triflate anion in organic solutions was theoretically confirmed with the identification of multiple ground state structures employing an implicit Solvation Model based on Density (SMD). Kinetics of nucleophilic attack of model glucosyl triflates by simple alcohol acceptors ethanol (EtOH) and trifluoroethanol (TFE), complexed with 2,4,6-tri--butylpyrimidine (TTBP) were explored, revealing the essential role of the close accompanying base for rendering glycosidic bond formation thermodynamically favorable. Our work deepens the comprehension of the glycosylation mechanism, paving the way for the rational design and future advancement of efficient and environmentally friendly stereoselective glycosylation reactions.
立体选择性化学糖基化反应是制备多种具有重要生物学和医学价值的化合物的关键,而化学糖基化反应的机理仍然模糊不清,大多是推测。在此,我们进行了 DFT 计算,以深入研究糖基化反应的多方面机理细节,包括溶液中反应性三酸甘油脂中间体之间的平衡、赋予保护基团的立体选择性、溶剂效应、碱和异构体效应。我们的研究结果为 2-OAc 邻位基团参与(NGP)、武装/解除武装效应、溶剂效应对糖基化立体化学的配位理论以及溶剂极性对跨越 S1-S2 连续体的反应动力学的影响提供了理论依据。利用基于密度的隐式溶解模型(SMD)识别了多个基态结构,首次从理论上证实了有机溶液中糖基氧羰基和三氟甲基阴离子的假定接触离子对(CIP)的存在。研究还探讨了 2,4,6-三丁基嘧啶(TTBP)与简单的醇受体乙醇(EtOH)和三氟乙醇(TFE)复合物对模型葡萄糖基三氟酸盐的亲核攻击动力学,揭示了密切伴随的碱在使糖苷键的形成在热力学上有利的关键作用。我们的工作加深了对糖基化机理的理解,为合理设计和未来推进高效、环境友好的立体选择性糖基化反应铺平了道路。
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引用次数: 0
Photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones: Synthesis of perfluoroalkyl chromones 邻羟基芳基烯酮的光诱导和电诱导全氟烷基化/环化:全氟烷基色酮的合成
Pub Date : 2024-03-13 DOI: 10.1016/j.gresc.2024.03.001
Shengjie Song, Wenjian Wang, Jun Sun, Can Luo, Chunlei Wu, Jianjun Li
A practical, metal-, and additive-free strategy for photo- and electro-induced perfluoroalkylation/cyclization of -hydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed. Various fluoroalkyl chromones were efficiently assembled in moderate to good yields. The scalability of this protocol and the assembling of diverse nitrogen-containing heterocycles from late-stage transformations of fluoroalkyl chromones greatly broaden the practical applications of this developed protocol.
本研究开发了一种实用的、无金属和添加剂的策略,用于在温和条件下用全氟烷基磺酸钠对-羟基芳基烯酮进行光诱导和电诱导全氟烷基化/环化。各种氟烷基色酮以中等至良好的产率被有效地组装起来。该方案的可扩展性以及通过氟烷基色酮的后期转化组装出各种含氮杂环的能力大大拓宽了该方案的实际应用范围。
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引用次数: 0
Enantioselective synthesis of planar chiral ferrocenes via gold(I)-catalyzed hydroarylation of N-ferrocenyl propiolamides 通过金(I)催化的 N-二茂铁基丙炔酰胺的加氢反应对平面手性二茂铁进行对映选择性合成
Pub Date : 2024-03-08 DOI: 10.1016/j.gresc.2024.02.007
Qian Zhou, Lulin Qiao, An-An Zhang, Lu Li, Tuan-Jie Meng, Baomin Fan, Yuan-Yuan Gao, Lantao Liu
Herein, we report an intramolecular cyclization of -ferrocenyl propiolamides for the synthesis of planar chiral ferrocenes enabled by gold(I)-catalyzed hydroarylation. By using this protocol, a variety of planar chiral ferrocenopyridin-2(1)-ones were obtained in good yields and excellent enantioselectivities (up to 96% ).
在此,我们报告了一种通过金(I)催化的氢化作用合成平面手性二茂铁的二茂铁丙酰胺分子内环化方法。通过该方法,我们获得了多种平面手性二茂铁吡啶-2(1)-酮,产量高,对映选择性极佳(高达 96%)。
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引用次数: 0
Mild and green thioacylation with dithiocarboxylates via photoredox catalysis 通过光氧化催化与二硫代羧酸进行温和绿色的硫代酰化反应
Pub Date : 2024-03-07 DOI: 10.1016/j.gresc.2024.02.008
Wen-Chao Gao, Wei Li, Juan Zhang, Hong-Hong Chang, Rong Zhou
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引用次数: 0
Palladium-catalyzed halosulfonylation of alkynes with ionic liquid as the green solvent and halide sources 以离子液体为绿色溶剂和卤化物源的钯催化炔烃卤磺化反应
Pub Date : 2024-02-26 DOI: 10.1016/j.gresc.2024.02.003
Yin-Long Lai, Li-Yun Wu, Xun Xiong, Yi-Wei Lan, Yin-Yun Lin, Rui-Min Zhong, Huanfeng Jiang, Jianxiao Li
The first palladium-catalyzed halosulfonylation of alkynes with arylsulfonic acid under aerobic conditions was accomplished. This catalytic protocol provides a straightforward and effective synthetic strategy for the assembly of structurally diverse -halovinyl sulfones architectures with high atom- and step-economy and exceptional functional group tolerance. Notably, ionic liquid plays a crucial role in this catalytic system, which not only acts as an environmentally friendly solvent, but also provides the halide source. In the presence of 1 mol % of IPr-Pd-Cin-Cl as the catalyst, a wide range of terminal alkynes and internal alkynes could be excellently tolerated. Particularly, the developed catalytic system could be recycled up to five times and reused without significant loss of catalytic activity.
首次在有氧条件下完成了炔烃与芳基磺酸的钯催化卤代磺酰化反应。该催化方案为组装结构多样的卤乙烯基砜结构提供了一种直接有效的合成策略,这种结构具有较高的原子和阶跃经济性以及优异的官能团耐受性。值得注意的是,离子液体在该催化体系中起着至关重要的作用,它不仅是一种环境友好型溶剂,还提供了卤化物源。在有 1 摩尔%的 IPr-Pd-Cin-Cl 作为催化剂的情况下,可以很好地耐受多种端基炔和内基炔。特别是,所开发的催化系统可以循环使用多达五次,而不会明显丧失催化活性。
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引用次数: 0
1,5-Pentanediol production from 3,4-dihydro-2H-pyran and acetic acid via successive reactions of esterification and hydrogenation 通过酯化和氢化连续反应从 3,4-二氢-2H-吡喃和乙酸中生产 1,5-戊二醇
Pub Date : 2024-02-24 DOI: 10.1016/j.gresc.2024.02.005
Siyuan Zhao, Hong Du, Qi Fang, Yuying Li, Lei Wu, Xiumei Liu, Feng Wang
1,5-Pentanediol as an important chemical intermediate is commonly used for the manufacture of polyesters and polyurethanes. A novel process was developed for the production of bio-based 1,5-pentanediol (1,5-PDO) from 3,4-dihydro-2H-pyran (DHP) and acetic acid (AA) in this work. The esterification of DHP and AA achieved a 59.8% DHP conversion and 91.2% tetrahydropyran-2-yl acetate selectivity (THPOAc) at 373 K for 1 h and DHP/AA molar ratio of 1 without catalyst. Then the 1,5-PDO with selectivity of 54.5% was obtained from THPOAc via hydrogenation over Cu/Zn/Al catalyst under the conditions of 453 K and 50 bar. The higher dispersion of Cu nanoparticles, the larger surface area of metallic Cu, the higher amount of Cu active sites and the lower acidity of Cu/Zn/Al catalyst were beneficial for the hydrogenation of THPOAc to 1,5-PDO.
1,5-戊二醇是一种重要的化学中间体,通常用于生产聚酯和聚氨酯。在这项工作中,开发了一种新工艺,利用 3,4-二氢-2H-吡喃(DHP)和乙酸(AA)生产生物基 1,5-戊二醇(1,5-PDO)。在不使用催化剂的情况下,DHP 和 AA 在 373 K 下酯化 1 小时,DHP 转化率达到 59.8%,四氢吡喃-2-基乙酸酯选择性(THPOAc)达到 91.2%。然后,在 453 K 和 50 bar 的条件下,在 Cu/Zn/Al 催化剂上进行加氢反应,从 THPOAc 中获得了选择性为 54.5% 的 1,5-PDO。Cu 纳米颗粒的较高分散度、较大的金属 Cu 表面积、较多的 Cu 活性位点以及 Cu/Zn/Al 催化剂的较低酸度都有利于 THPOAc 加氢生成 1,5-PDO。
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引用次数: 0
Rapid access to diverse indoles by addition/SNAr with grignard reagents and 2-fluorophenyl acetonitriles 通过与格氏试剂和 2-氟苯基乙腈的加成/SNAr 快速获得各种吲哚
Pub Date : 2024-02-24 DOI: 10.1016/j.gresc.2024.02.004
Yuanyun Gu Gu, Yaxin Feng, Baotong Huang, Yan-En Wang, Yaqi Yuan, Dan Xiong, Yonghong Hu, Xiufang Xu, Patrick J. Walsh, Jianyou Mao
Indoles are essential heterocycles in natural products, biological chemistry, and medicinal chemistry. Efficient approaches to their synthesis, therefore, remain in demand. Herein is reported a novel and scalable method to produce a wide variety of indoles by combining Grignard reagents and 2-fluorobenzyl cyanides (59 examples, 45–95% yields). The Grignard reagent adds to the nitrile to give a metalated imine that undergoes SAr with unactivated C–F bonds. This strategy installs the R group of RMgX at the indole 2-position, and it is noteworthy that a diverse array of Grignard reagents (aryl, alkyl, vinyl, and cyclopropyl) provide the desired heterocyclic products. The resulting -magnesiated indole can be in situ functionalized at the 3-position with alkyl halides or functionalized on the nitrogen with silyl chlorides. This method enables the synthesis of indoles with functional groups at each position of the indole backbone (C4–C7), providing handles for further functionalization.
吲哚是天然产物、生物化学和药物化学中不可或缺的杂环。因此,仍然需要高效的合成方法。本文报道了一种新颖且可扩展的方法,通过结合格氏试剂和 2-氟苄基氰化物(59 个实例,产率 45-95%)来生产各种吲哚。格氏试剂加入腈中生成金属化亚胺,该亚胺与未活化的 C-F 键发生 SAr 反应。值得注意的是,各种格氏试剂(芳基、烷基、乙烯基和环丙基)都能提供所需的杂环产物。生成的镁化吲哚可在 3 位上用烷基卤化物进行原位官能化,或在氮上用硅基氯化物进行官能化。这种方法可以合成在吲哚骨架的每个位置(C4-C7)都带有官能团的吲哚,为进一步官能化提供了途径。
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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 : 2024-02-23 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
{"title":"Synthesis of bridged bicyclic thiazine-2-thione and thiazole-2-thiones through DBU-promoted regioselective annulation of quinone monoacetals under mild conditions","authors":"Hong Qin, Man Yang, Yuguang Li, Xiaobing Yang, Yujing Hu, Chengkou Liu, Wei He, Zheng Fang, Kai Guo","doi":"10.1016/j.gresc.2023.12.004","DOIUrl":"https://doi.org/10.1016/j.gresc.2023.12.004","url":null,"abstract":"","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139946967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Green Synthesis and Catalysis
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