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Copper-catalyzed oxidative intramolecular cyclization for the synthesis of 2-hydroxy-indolin-3-ones 铜催化氧化分子内环化合成 2-羟基-吲哚啉-3-酮
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-11 DOI: 10.1002/adsc.202400493
Haojie Ma, Fengyuan Zhou, Yuqi Li, Yuqi Zhang, Guosheng Huang, Xing Yang, Ji-Jiang Wang
The synthesis of substituted 2-hydroxy-indolin-3-ones has attracted considerable attention due to the frequent presence of the indole nucleus in numerous natural products and biologically active molecules. Herein, a direct access to 2-hydroxy-indolin-3-ones through copper-catalyzed oxidative intramolecular cyclization of N-(2-acetylphenyl)picolinamide has been developed. This method exhibits good functional group tolerance, atom-economy and avoids the pre-functionalization of substrates.
由于许多天然产物和生物活性分子中经常出现吲哚核,取代的 2-羟基-吲哚啉-3-酮的合成引起了广泛关注。本文开发了一种通过铜催化 N-(2-乙酰苯基)吡啶酰胺的氧化分子内环化直接获得 2-羟基-吲哚啉-3-酮的方法。该方法具有良好的官能团耐受性和原子经济性,并避免了底物的预官能化。
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引用次数: 0
Pd-Catalyzed Allylic Substitution using Nucleophilic Amines: Access to Functionalized Mono- and Bis-N-Allyl Synthons 使用亲核胺的钯催化烯丙基取代反应:获得功能化的单-和双-N-烯丙基合成物
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-09 DOI: 10.1002/adsc.202400685
Fengyun Gao, Debasish Ghorai, Jordi Benet-Buchholz, Arjan Kleij
We here report a catalytic strategy to enable the decarboxylative allylic amination of vinyl cyclic carbonates using various aliphatic and nucleophilic amines. The use of a protic medium and chelating diphosphine ligands is a main driver towards chemo-selective allylicamine formation, thereby minimizing undesired ligand-driven complex speciation and aminolysis of the involved substrate. This improved approach amplifies the repertoire of allylic amine synthons that can be prepared from a variety of substrate combinations.
我们在此报告一种催化策略,利用各种脂肪族和亲核胺对乙烯基环状碳酸酯进行脱羧烯丙基胺化反应。使用原生介质和螯合二膦配体是形成化学选择性烯丙基胺的主要驱动力,从而最大程度地减少了配体驱动的不需要的络合物分化和相关底物的氨基分解。这种改进的方法扩大了烯丙基胺合成物的范围,可以从多种底物组合中制备烯丙基胺。
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引用次数: 0
Nickel-Catalyzed Cross-Coupling of Aryl alkyl Selenides with Aryl Bromides: Cross Coupling between two electrophile 镍催化的芳基烷基硒化物与芳基溴化物的交叉偶联:两个亲电体之间的交叉偶联
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-09 DOI: 10.1002/adsc.202400707
Sumit Kumar, Shivani Sapra, Brajendra Singh
A nickel-catalyzed cross-coupling reaction has been developed using two distinct electrophiles: an aryl alkyl selenide and an aryl bromide. The organoselenium compound, due to the lower bond dissociation energy of the C-Se bond, acts as a pseudohalide. This one-pot reaction proceeds by cleaving the C-Se bond, producing the desired biaryls in moderate to good yields. This method has the potential to become a valuable tool in organic synthesis, owing to its substrate scope and scalability. Importantly, the use of commercially available aryl bromides eliminates the handling of pre-formed organomagnesium reagents, enhancing the practicality and applicability of this approach.
我们开发了一种镍催化交叉偶联反应,使用了两种不同的亲电剂:芳基烷基硒化物和芳基溴化物。由于 C-Se 键的键解离能较低,有机硒化合物起到了假卤化物的作用。这种一锅反应通过裂解 C-Se 键进行,以中等至较高的产率生成所需的双芳基化合物。这种方法具有底物范围广和可扩展性强的特点,有望成为有机合成的重要工具。重要的是,使用市场上可买到的芳基溴化物无需处理预先形成的有机镁试剂,从而提高了这种方法的实用性和适用性。
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引用次数: 0
Decarboxylative Aminomethylation of Ferulic Acids via Visible‐Light‐Promoted Flavin Photocatalysis and its Application in the Synthesis of Anti‐Inflammatory Lead Compounds 通过可见光促进的黄素光催化对阿魏酸进行脱羧氨甲基化及其在抗炎铅化合物合成中的应用
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-08 DOI: 10.1002/adsc.202400596
Lin Wang, Xinye Lv, Lei Huang, Yingxue Yang, Xiaomei Ge, Jianguo Zeng, Pi Cheng
Herein, we reported a protocol for direct visible‐light‐mediated decarboxylative aminomethylation of ferulic acid with N‐aryl tetrahydroisoquinolines in air atmosphere. Current protocol uses naturally available ferulic acid as coupling partner, inexpensive organic photocatalyst riboflavin tetraacetate (RFTA) as photocatalyst and molecular oxygen as oxidant, which is suitable for late‐stage functionalization of complex nitrogen‐containing molecules. This methodology was further demonstrated its utility by the protecting‐group‐free semi‐synthesis of natural alkaloids maclekarpine E and assessing the anti‐inflammatory activity of its analogues.
在此,我们报告了一种在可见光介导下,阿魏酸与 N-芳基四氢异喹啉在空气中直接发生脱羧氨基甲基化反应的方法。目前的方案以天然阿魏酸为偶联剂,以廉价的有机光催化剂四乙酸核黄素(RFTA)为光催化剂,以分子氧为氧化剂,适用于复杂含氮分子的后期功能化。通过无保护基半合成天然生物碱马钱子碱 E 及其类似物的抗炎活性评估,进一步证明了该方法的实用性。
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引用次数: 0
Light‐Induced Iodine‐Catalyzed Dealkylative Synthesis of Enaminones 光诱导碘催化的烯丙酮脱烷基合成反应
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-08 DOI: 10.1002/adsc.202400631
Mingming Zhao, Luyao Wang, Yufeng Zhou, Fenke Guo, Tao Yang, Heng-Ying Xiong, Teng Wang, Guangwu Zhang
Light mediated iodine catalyzed synthesis of enaminones through C‐N bond cleavage has been described. In addition to substituted ynones, diverse substituted acyclic tertiary amines, and cyclic tertiary amines were also reactive under standard conditions. Selected transformations of the coupling adduct demonstrated the latent utility of this protocol. Preliminary mechanistic studies were also conducted.
通过 C-N 键裂解,描述了光介导的碘催化合成烯酮。在标准条件下,除取代的炔酮外,各种取代的无环叔胺和环叔胺也能发生反应。耦合加合物的部分转化证明了这一方案的潜在用途。此外,还进行了初步的机理研究。
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引用次数: 0
Enzymatic Dimerization of Fungal Natural Products through Intermolecular Disulfide Bridges 通过分子间二硫桥实现真菌天然产物的酶促二聚化
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-07 DOI: 10.1002/adsc.202400671
Jarukitt Limwachiranon, Fan Xu, Liru Xu, Zhenzhen Xiong, Yi Han, Yaojie Guo, Nan Zhang, Daniel H Scharf
The biosynthetic pathway for the production of natural products from various species often include a dimerization step which increases the structural variability and range of biological activities. These dimerization reactions are highly interesting for biocatalytic applications. Epipolythiodioxopiperazines (ETPs) are an important class of natural products whose potent bioactivities rely on disulfide bridges. ETPs often carry a transannular disulfide bridge and can be linked through C–C and C–N bonds to form dimers. In this study, we shed light on the mechanism of disulfide formation in the case of the dimeric vertihemiptellides (vhe) produced by the fungus Verticillium hemipterigenum BCC1449. These compounds feature a unique intermolecular disulfide bridge which links two monomers together. Using comparative genomics, we identified the 12-membered vhe gene cluster. In vitro assays, kinetic analysis, and protein mutagenesis, enabled us to characterize VheT, the oxidase catalyzing an intermolecular disulfide bond formation resulting in ETP dimers. We showed that the CxxC motif of VheT plays a crucial role in catalyzing this reaction. VheT is an oxidase linking natural product monomers through intermolecular S–S bridges and could be developed into a biocatalyst for thiol specific dimerization reactions.
从不同物种中生产天然产物的生物合成途径通常包括二聚化步骤,这增加了结构的可变性和生物活性的范围。这些二聚化反应对于生物催化应用非常有意义。表硫基二氧哌嗪(ETPs)是一类重要的天然产物,其强大的生物活性依赖于二硫桥。ETPs 通常带有跨annular 二硫桥,并可通过 C-C 和 C-N 键连接形成二聚体。在本研究中,我们揭示了由真菌 Verticillium hemipterigenum BCC1449 产生的二聚体 vertihemiptellides (vhe) 的二硫化物形成机制。这些化合物具有独特的分子间二硫桥,可将两个单体连接在一起。通过比较基因组学,我们确定了 12 元 vhe 基因簇。通过体外实验、动力学分析和蛋白质诱变,我们确定了 VheT 的特征,它是催化分子间二硫键形成 ETP 二聚体的氧化酶。我们发现,VheT 的 CxxC 基序在催化这一反应中起着关键作用。VheT 是一种通过分子间 S-S 桥连接天然产物单体的氧化酶,可以开发成一种用于硫醇特异性二聚化反应的生物催化剂。
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引用次数: 0
Copper-Catalyzed Chan-Lam Reaction and Sequential [2,3]-Rearrangement to Prepare α-Benzotriazinium Ketones 铜催化 Chan-Lam 反应和顺序 [2,3]- 重排制备 α-苯并三嗪酮
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-07 DOI: 10.1002/adsc.202400639
Jia-Yi Gao, Meng-Yan Wei, Xian-Jun Wei, Hong-Yan Bi, Cui Liang, Chun-Hua Chen, Dong-Liang Mo
A variety of α-benzotriazinium ketones were prepared in 38%-89% yields through a copper(II)-catalyzed Chan-Lam reaction and [2,3]-rearrangement in a one pot reaction open to air from N-hydroxybenzotriazin-4-ones and alkenyl boronic acids at room temperature. Experimental results showed that the copper catalyst not only played as cross-coupling catalyst but also served as Lewis acid catalyst to control the chemoselectivity of [2,3]-rearrangement. The reaction tolerated various linear and cyclic disubstituted alkenyl boronic acids. Moreover, α-benzotriazinium ketone could be easily prepared in gram scales. The present method highlights dual roles of copper catalyst and [2,3]-rearrangement of N,O-vinyl moiety.
在铜(II)催化下,N-羟基苯并三嗪-4-酮和烯基硼酸在室温下进行了Chan-Lam反应和[2,3]重排反应,以38%-89%的收率制备了多种α-苯并三嗪酮。实验结果表明,铜催化剂不仅可以作为交叉偶联催化剂,还可以作为路易斯酸催化剂控制 [2,3] 重排反应的化学选择性。该反应可容忍各种线性和环状二取代烯基硼酸。此外,α-苯并三嗪酮可在克级范围内轻松制备。本方法突出了铜催化剂和 N,O-乙烯基[2,3]重排的双重作用。
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引用次数: 0
Lewis Base Controlled (4 + 3) and (4 + 2) Annulations of MBH Carbonates with Benzofuran‐derived Azadienes: Access to Highly Substituted Benzofuro[3,2‐b]azepines and Spirotetrahydroquinolines 路易斯碱控制(4 + 3)和(4 + 2)MBH 碳酸酯与苯并呋喃衍生的偶氮二烯的嵌合:获得高取代的苯并呋喃并[3,2-b]氮杂卓和螺四氢喹啉
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-07 DOI: 10.1002/adsc.202400712
Kai-Kai Wang, Ya-Fei Li, Lan-Xin Li, Wei-Wei Yao, Yan-Li Li, Ran Bi, Feng Li, Xiao-Long He, Rongxiang Chen
Catalyst‐controlled switchable (4 + 3) and (4 + 2) annulation reactions of Morita–Baylis–Hillman carbonates with benzofuran‐derived azadienes have been established. Employing PCy3 as the catalyst, the reaction could provide a variety of synthetically useful benzofuro[3,2‐b]azepines in good yields (80‐92%) with excellent chemo‐ and regioselectivities via (4 + 3) cycloaddition reactions. Whereas changing the catalyst from PCy3 to DMAP, the chemo‐ and regioselectivities were switched to construct highly substituted spirotetrahydroquinoline scaffolds with three sequential stereocenters containing all‐carbon spiro‐quaternary stereocenters in excellent efficiency and diastereoselectivities (92‐96% yields with all cases > 25:1 dr) via (4 + 2) annulations. In addition, the synthetic utility of this method was further showcased by gram‐scale reactions and synthetic transformations of the product.
研究人员建立了莫里塔-贝利斯-希尔曼碳酸盐与苯并呋喃衍生氮杂二烯的催化剂可控切换式(4 + 3)和(4 + 2)环化反应。该反应采用 PCy3 作为催化剂,通过 (4 + 3) 环加成反应可以提供多种对合成有用的苯并呋喃并[3,2-b]氮杂卓,产率高(80-92%),化学选择性和区域选择性极佳。将催化剂从 PCy3 改为 DMAP 后,化学选择性和区域选择性发生了变化,从而通过 (4 + 2) 环化反应构建了具有三个连续立体中心的高取代螺四氢喹啉支架,这些支架含有全碳螺季立体中心,具有极佳的效率和非对映选择性(产率为 92-96%,所有情况下均为 25:1)。此外,通过克级反应和产物的合成转化,进一步展示了该方法的合成实用性。
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引用次数: 0
Recent Advances and Prospects in Manganese‐Catalyzed C‐H Activation 锰催化 C-H 活化的最新进展和前景
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-06 DOI: 10.1002/adsc.202400611
Gopan Anusree, P. S. Devi, Gopinathan Anilkumar
C–H activation represents an interesting alternative to conventional cross‐coupling methods, avoiding the requirement of additional steps to introduce activating groups. Generally, Pd‐catalyzed reactions have been extensively employed for C–H activation. The high cost and limited availability of resources of Pd have prompted us to explore alternative transition metals. In this context, researchers are turning to Earth Abundant Metals (EAMs) like manganese and iron for their potential in C–H activation.Significant progress has been made in manganese‐catalyzed C–H activation in recent years, showcasing excellent specificity, environmental compatibility, and versatility across different substrates. This review summarizes approximately 50 recent publications highlighting significant advancements in this field from 2020 to 2023.
C-H 活化是传统交叉偶联方法的一种有趣的替代方法,它避免了引入活化基团的额外步骤。一般来说,钯催化反应已被广泛用于 C-H 活化。钯的高成本和有限资源促使我们探索其他过渡金属。近年来,锰催化 C-H 活化技术取得了重大进展,显示出卓越的特异性、环境相容性和在不同基质中的通用性。本综述总结了 2020 年至 2023 年期间约 50 篇近期发表的论文,重点介绍了这一领域的重大进展。
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引用次数: 0
Dearomative Functionalization of Activated Quinolines: Transfer Hydrogenation/Cycloaddition Cascade to Construct α-Tertiary Amines 活化喹啉类化合物的氢化官能化:通过转移氢化/环加成级联构建 α-叔胺
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-08-06 DOI: 10.1002/adsc.202400770
Suman Yadav, Ruchir Kant, Malleswara Rao Kuram
Cascade dearomative functionalization is a robust protocol to convert flat arenes into medicinally relevant three-dimensional architectures with added new functionality. Herein, a dearomative cycloaddition protocol for synthesizing tetrahydroquinoline-embedded α-tertiary amine scaffolds has been developed employing quinolinium salts and sulfonyl azides under metal-free conditions. An underexplored and mechanistically distinct pathway is unveiled, creating quaternary-center-bearing amine skeletons by an amine group migration during the transfer hydrogenation and cycloaddition cascade reaction. This approach provided a broad substrate scope of α-tertiary amine scaffolds from a plethora of C3-substituted quinolinium and sulfonyl azides. The post-synthetic modifications have further diversified the α-tertiary amine core into interesting scaffolds. Preliminary mechanistic studies suggested the involvement of aziridine ring formation for the amine migration to the C-3 position of quinoline to generate the α-tertiary amine core.
级联脱芳香族官能化是将扁平烷烃转化为具有新功能的药用三维结构的可靠方案。在此,我们开发了一种脱芳香环加成协议,利用喹啉盐和磺酰叠氮化物在无金属条件下合成嵌入四氢喹啉的 α-叔胺支架。在转移氢化和环加成级联反应过程中,通过胺基团的迁移,产生了以四元为中心的胺骨架。这种方法从大量 C3 取代的喹啉和磺酰叠氮化物中提供了广泛的 α-叔胺支架底物。合成后修饰使 α-叔胺核心进一步多样化,形成了有趣的支架。初步的机理研究表明,氮丙啶环的形成参与了胺向喹啉 C-3 位的迁移,从而生成了 α-叔胺核心。
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引用次数: 0
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