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Insight into the Key Factors that Influence the Reaction Pathways in the Silyl‐Prins Cyclization of gem‐Vinylsilyl Alcohols 影响宝石-乙烯基硅醇硅-普林斯环化反应途径关键因素的研究
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401437
Paula González‐Andrés , Carlos Díez‐Poza , Laura F. Peña , Daniel Gónzalez‐Pinardo , Israel Fernández , Asunción Barbero
This work provides an in‐depth analysis of the factors governing the different reaction pathways in the acid‐catalyzed cyclization of gem‐vinylsilyl alcohols with aldehydes. The study evaluates the impact of both the ligands attached to silicon and the choice of the Lewis acid on the reaction outcome. Additionally, computational studies offer valuable insights into the mechanism that control these distinct pathways. The process enables the chemo‐ and stereocontrolled formation of a variety of structural frameworks, offering significant potential for the generation of a broad range of molecular architectures.
这项工作提供了一个深入的分析因素,在酸催化的宝石乙烯基硅醇与醛环化的不同反应途径。本研究评估了硅的配体和路易斯酸的选择对反应结果的影响。此外,计算研究为控制这些不同途径的机制提供了有价值的见解。该工艺使化学和立体控制形成各种结构框架成为可能,为产生广泛的分子结构提供了巨大的潜力。
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引用次数: 0
Copper‐Powder‐Mediated Tandem Hydroamination Cyclization‐Hydrocyanation of Alkyne‐Tethered Ketoximes Toward Cyano‐Substituted Cyclic Nitrones 铜粉介导的炔烃系酮肟的串联氢化环化-氢化氰化反应,生成具有氰基特征的环状硝基化合物
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401049
Wen‐Jun Han , Fang‐Long Yang , Zhiyuan Hu , Wenxia Chen , Shun Liu , Ke Guo , Xin‐Yuan Yang , Bin Cheng
A copper‐powder‐mediated tandem hydroamination cyclization–hydrocyanation of alkyne‐tethered ketoximes is described by using TMSCN as a commercially available cyanating reagent. This methodology provides an alternative strategy for the synthesis of a series of structurally important cyano‐substituted cyclic nitrones. The hydrocyanation process exhibits distinct regioselectivity depending on the substituent pattern of the alkyne moiety. Moreover, the synthesized products were shown to be capable of undergoing various derivatization reactions.
以 TMSCN 作为市售氰化试剂,介绍了铜粉介导的炔烃系酮肟的串联氢化环化-氢氰化反应。这种方法为合成一系列结构重要的氰基取代环腈提供了另一种策略。根据炔基的取代基模式,氢氰化过程表现出明显的区域选择性。此外,合成的产物还能进行各种衍生反应。
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引用次数: 0
Photocatalytic C−I Bond Borylation and Phosphorylation of Diaryliodonium Salts with Excellent Atom‐Economy 具有优异原子经济性的二芳基碘鎓盐的光催化C-I键硼化和磷酸化
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401240
Tian‐Yu Ding , Xiao‐Ning Guo , Bin Chen , Chen‐Ho Tung , Li‐Zhu Wu
Highly atom‐economic conversion of diaryliodonium salts represents an underdeveloped but highly desirable domain. Most reactions involving these species only utilize single aryl group of the diaryliodonium salts and produce an equivalent of aryl iodide as waste. Herein, by further transforming the side‐product aryl iodide, we report an overall new two‐step one‐pot strategy that allows photocatalytic C−I bond borylation of diaryliodonium salts and ensures effective conversion of both aryl groups of the diaryliodonium into the relevant arylboronic esters. Mechanistic investigations suggest that electron‐donor‐acceptor complex is formed between the photocatalyst phenothiazine and diaryliodonium salt substrate. Upon visible light irradiation, this complex produces aryl radical and aryl iodide. With addition of a base in the second step, the reducing ability of the photocatalyst is enhanced via proton‐coupled electron transfer process, thereby aryl iodide produced in the first step is reduced to yield aryl radical again. Both aryl radicals generated in the two steps react with B2(OR)4 to produce the corresponding monoarylation product in a quantitative yield. The strategy is also applicable for C−I bond phosphorylation of diaryliodonium salts, ensuring that both aryl moieties can be phosphorylated with high efficiency.
高原子经济性的二芳基碘鎓盐转化是一个不发达但非常理想的领域。大多数涉及这些物种的反应只利用二芳基碘的单个芳基,并产生相当于碘化芳基的废物。在此,通过进一步转化副产物芳基碘化物,我们报告了一种全新的两步一锅策略,该策略允许光催化二芳基碘鎓盐的C - I键硼化和磷酸化,并确保二芳基碘鎓的两个芳基有效转化为相关的芳基硼酯或芳基膦酯。机理研究表明,在光催化剂吩噻嗪(PTH)和二芳基碘鎓盐底物之间形成电子给受体(EDA)络合物。在可见光照射下,该络合物产生芳基自由基和芳基碘化物。第二步加入碱后,通过质子耦合电子转移(PCET)过程增强光催化剂的还原能力,从而使第一步产生的芳基碘化物再次还原生成芳基自由基。这两步生成的芳基自由基均与B2(OR)4或P(OR)3反应,定量生成相应的单芳基化产物。
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引用次数: 0
Ruthenium(II)‐Catalyzed Pyridyl‐Directed Tryptophan C−H Acylmethylation with α‐Chloro Ketones 钌(II)催化的吡啶基引导的α-氯酮色氨酸 C-H 乙酰甲基化反应
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400947
Shulei Hu , Yong Wang , Xiong Xie , Renwen Liang , Hong Liu , Jiang Wang
A ruthenium(II)‐catalyzed C−H acylmethylation of Trp‐containing peptides with α‐chloro ketones is reported here. This reaction features good C‐2 selectivity and chemoselectivity, making it suitable for late‐stage modification of Trp‐containing peptides. Low‐cost metal ruthenium as a catalyst enables the reaction to be conducted on a gram scale. This report also discusses the synthetic applications and presents a method to remove the pyridine directing group. In addition, a plausible mechanism of the C(2)−H acylmethylation reaction is proposed in this article.
据报道,钌(Ⅱ)催化的含 Trp 肽与α-氯酮的 C-H酰甲基化反应具有良好的 C-2 选择性和化学选择性,使其适用于含 Trp 肽的后期修饰。该反应具有良好的 C-2 选择性和化学选择性,因此适用于含 Trp 肽的后期修饰。低成本的金属钌作为催化剂,使该反应可以在克级规模上进行。本报告还讨论了合成应用,并介绍了去除吡啶二定向基团的方法。此外,本文还提出了 C(2)-H酰甲基化反应的合理机理。
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引用次数: 0
Direct Synthesis of 3,4‐Disubstituted Quinolines and 2‐Acylquinolines from Amines and Epoxides 从胺和环氧化物直接合成 3,4-二取代喹啉和 2-酰基喹啉
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401055
Xueyan Lv , Shichen Li , Shuai Fang , Xiaotian Wu , Bingchuan Yang , Chen Ma
Herein, we present a protocol starting from styrene oxide reacting with o‐acylaniline and o‐alkenylaniline derivatives to obtain 3,4‐disubstituted quinoline and 2‐acylquinoline derivatives, respectively, in 32–92% yields under specific conditions. Preliminary research outcomes underscore the versatility of our approach, as exemplified by its scalability for large‐scale synthesis, downstream derivatization, and the characteristic properties manifested by the modified molecules.
在本文中,我们介绍了一种以氧化苯乙烯为起点,与邻-酰基苯胺和邻-烯基苯胺衍生物反应,在特定条件下分别获得 3,4-二取代喹啉和 2-酰基喹啉衍生物的方法,产率为 32-92%。初步研究成果强调了我们的方法的多功能性,例如它在大规模合成、下游衍生化方面的可扩展性,以及改性分子所表现出的特性。
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引用次数: 0
CuF2‐Catalyzed C‐N Cross‐Coupling of Aryl Silanes: Expanding the Scope of Chan‐Lam Type Reaction
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401498
Vishal Talukdar, Siddhartha Paul, Krishanu Mondal, Parthasarathi Das
An efficient copper‐catalyzed Chan–Lam type N‐arylation of various amides, sulfonamides, urea, azoles, and amines has been demonstrated using a CuF2/DMSO catalytic system with structurally diverse aryl(trimethoxy)silanes under base and ligand‐free conditions. This approach facilitates effective C‐N cross‐coupling with user‐friendly organosilicon reagents without requiring an external fluoride source. CuF2 serves a dual function as both a catalyst and a desilylating agent, facilitating the cleavage of the aryl‐silane bond. The process is compatible with a broad range of substrates, ensuring high efficiency and excellent functional group compatibility. Moreover, this protocol is proven to be valuable for late‐stage modification of amide and sulfonamide‐containing drug molecules, as well as for synthesizing agrochemicals.
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引用次数: 0
Synergistic Palladium/Silver/Ligand Catalysis for C−H Alkenylation of 2,1,3‐Benzofused Heterodiazoles 钯/银/配体协同催化 2,1,3-苯并二唑的 C-H 烯化反应
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401139
Siyeon Jeong , Chaerin Lee , Jung Min Joo
The combination of palladium and silver complexes has emerged as a bimetallic catalytic system in C−H activation, frequently outperforming palladium‐only systems. Beyond the conventional roles of silver (I) salts serving as oxidants, halide scavengers, and Lewis acids, Pd−Ag bimetallic synergism has been shown to facilitate C−H cleavage. In this study, we explore the incorporation of a pyrazolopyridone (PzPyOH) ligand into a Pd−Ag bimetallic catalytic system, which together promote both C−H cleavage and migratory insertion processes. This synergistic approach enables dehydrogenative C−H alkenylations at the C4 position of 2,1,3‐benzothiadiazole, 2,1,3‐benzoxadiazole, and 2,1,3‐benzotriazole with alkenes. These results demonstrate the potential of combining novel ligands with heterobimetallic systems to facilitate other elementary steps beyond C−H cleavage, suggesting their broader applicability in C−H functionalization.
钯和银络合物的组合已成为 C-H 活化的双金属催化体系,其性能经常优于纯钯体系。除了银 (I) 盐作为氧化剂、卤化物清除剂和路易斯酸的传统作用外,钯银双金属协同作用已被证明可促进 C-H 裂解。在本研究中,我们探讨了在钯银双金属催化体系中加入吡唑吡啶酮(PzPyOH)配体,从而共同促进 C-H 裂解和迁移插入过程。这种协同方法使 2,1,3-苯并噻二唑、2,1,3-苯并噁二唑和 2,1,3-苯并三唑在 C4 位与烯烃发生脱氢 C-H 烯化反应。这些结果表明,将新型配体与杂多金属系统结合起来,可以促进 C-H 裂解以外的其他基本步骤,这表明它们在 C-H 功能化方面具有更广泛的适用性。
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引用次数: 0
Tandem Photocatalyst‐Free Visible Light Aryl Azidation‐Intramolecular C−H Amination: One‐Pot Access to Carbazoles and Indoles from Areneazo‐2‐(2‐nitro)propanes 串联无光催化剂可见光芳基叠氮化-分子内C - H胺化:从2-(2-硝基)丙烷中获得咔唑和吲哚的一锅方法
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401333
Dilip V. Patil , Rahulkumar Patel , Shinobu Takizawa , Hun Y. Kim , Kyungsoo Oh
The visible light‐induced one‐pot tandem photolysis of areneazo‐2‐(2‐nitro)propanes was achieved to give carbazole and indole derivatives. The aryl azidation followed by an intramolecular C−H amination smoothly proceeded under visible light irradiation without any photocatalyst, demonstrating the synthetic versatility of areneazo‐2‐(2‐nitro)propanes. The in situ generation of aryl azide intermediates was executed under mild visible light photolysis conditions, showcasing the synthetic versatility of areneazo‐2‐(2‐nitro)propanes, a safe alternative of diazonium salts.
采用可见光诱导的单锅串联光解法,制备了咔唑和吲哚衍生物。在没有任何光催化剂的情况下,芳基叠氮化和分子内C - H胺化在可见光照射下顺利进行,证明了芳烃偶氮-2-(2-硝基)丙烷的合成通用性。在温和的可见光光解条件下原位生成芳基叠氮化物中间体,展示了重氮盐的安全替代品-芳氮偶氮-2-(2-硝基)丙烷的合成通用性。
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引用次数: 0
First Bromide‐Catalyzed Selenylation of 2‐Alkyn‐1‐One O‐Methyloximes Enabled the Synthesis of 4‐Selenylated Isoxazoles 第一溴化物催化2 -炔- 1 - 1 - O -甲基肟的硒化使4 -硒化异恶唑的合成成为可能
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401477
Jinhui Cai , Zhouting Zeng
A series of 3,5‐diaryl‐4‐selanylisoxazoles were synthesized in 56–97% yields (most cases>80% yield), which was first accomplished via bromide‐catalyzed selenylation of 2‐alkyn‐1‐one O‐methyloximes using element Se and boronic acids as the selenyl source. Compared to traditional strategies, this method proceeded under simple catalytic system. Broad substrate scope, good functional group compatibility, metal‐free conditions, and easy operation was showed in this protocol. Additionally, this method was easily amendable to gram‐scale reaction and synthetic transformations. Furthermore, preliminary mechanistic experiments demonstrated that a radical pathway was possibly involved in this work.
以硒元素和硼酸为硒基源,通过溴催化2 -炔- 1 - 1 O -甲基肟的硒化反应,合成了一系列3,5 -二芳基- 4 - selanyillisoxazoles,产率为56 - 97%(大多数产率为80%)。与传统方法相比,该方法在简单的催化体系下进行。该方案具有底物范围广、官能团相容性好、无金属条件、操作简便等特点。此外,该方法易于进行克尺度反应和合成转化。此外,初步的机制实验表明,自由基途径可能参与了这项工作。
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引用次数: 0
Dual C2 Synthon Strategy for the Synthesis of Pyrimidines: Copper‐Catalyzed Aerobic α,β‐C(sp3)−H Bond Difunctionalization of Tertiary Alkylamines 合成嘧啶的双 C2 合成策略:铜催化三级烷基胺的α,β-C(sp3)-H 键双官能化
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400907
Ramachandra Reddy Putta , Junhwa Hong , Seung Hyun Choi , Jinwoo Lee , Honghui Lee , Seok Beom Lee , Suckchang Hong
Herein, we describe a two‐component methodology developed for the synthesis of pyrimidine derivatives using tertiary alkylamines and amidines. Tertiary alkylamines serve as dual C2 synthons through copper‐catalyzed aerobic difunctionalization of the α,β−C(sp3)−H bonds. The process operates under mild conditions and uses atmospheric oxygen as the oxidant. Notably, by this methodology yields up to 85% yields are obtained and a broad substrate scope is shown. Mechanistic studies indicate that the annulation proceeds via a radical‐mediated oxidation and C−N bond coupling process. This approach provides a pathway for synthesizing various heterocycles by employing tertiary alkylamines as dual C2 synthons.
在此,我们介绍一种利用叔烷基胺和脒合成嘧啶衍生物的双组分方法。通过铜催化α,β-C(sp3)-H 键的有氧双官能化,叔烷基胺可作为双 C2 合物。该过程在温和的条件下进行,使用大气中的氧气作为氧化剂。值得注意的是,这种方法的产率高达 85%,并显示出广泛的底物范围。机理研究表明,环化是通过自由基介导的氧化和 C-N 键偶联过程进行的。这种方法为利用叔烷基胺作为双 C2 合物合成各种杂环提供了途径。
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引用次数: 0
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Advanced Synthesis & Catalysis
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