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Synthesis of Difuropyridines from Chitin-Derived 3-Acetamidofuran and their Application to Photocatalytic Reactions 从甲壳素衍生的 3-乙酰氨基呋喃合成二呋啶类化合物及其在光催化反应中的应用
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-18 DOI: 10.1002/adsc.202401164
Haifeng Gan, Peipei Ma, Taixiang Yang, Fei Cao, Jianliang Zhu

Difuropyridines have been prepared from aldehydes and chitin-derived 3-acetamidofuran (3AF) under acid-catalyzed conditions. Difuropyridines were comprehensively synthesized for the first time. The synthesized difuropyridines can be applied to prepare fluorescent probe analogs or catalyze decarboxylative reactions as photocatalysts.

在酸催化条件下,由醛和甲壳素衍生的 3-乙酰胺基呋喃(3AF)制备了二糠基吡啶。这是首次全面合成二呋啶类化合物。合成的二糠基吡啶可用于制备荧光探针类似物或作为光催化剂催化脱羧反应。
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引用次数: 0
The Chemistry of α-Enolizable Alkynones: a Comprehensive Review 可烯化的α-炔酮化学:全面回顾
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-18 DOI: 10.1002/adsc.202401312
Sofia Karnakova, Marina Dvorko, Dmitrii Shabalin
This comprehensive review summarizes the published literature data concerning the chemistry of α-enolazible alkynones, also denoted aliphatic or C-H active alkynones, where an alkyl group is adjacent to the carbonyl function, from the first example in 1949 to the present day. Starting from a historical perspective, the reader will be introduced to the recent achievements and future challenges in this field. The review covers around 100 references.
这篇综合性综述总结了从 1949 年第一个实例到今天已发表的有关 α-烯唑可炔酮(也称脂肪族或 C-H 活性炔酮,其中烷基与羰基功能相邻)化学的文献资料。从历史角度出发,读者将了解到该领域的最新成就和未来挑战。该综述涵盖约 100 篇参考文献。
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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 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-18 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
Synthesis of Functionalized Benzo[f]chromanes and Hydroxyalkyl Naphthols: Catalytic Coupling of Naphthols and Allylic Alcohols 功能化苯并[f]色烷和羟基烷基萘酚的合成:萘酚和烯丙基醇的催化偶联
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-18 DOI: 10.1002/adsc.202401243
Raman Sankar, Chidambaram Gunanathan
Catalytic dearomatization of arenols is an uphill task that can serve as a powerful method to construct C-C bonds with unsaturated coupling partners. Herein, a simple and efficient strategy for coupling naphthols with allylic alcohols is reported. A single Ru(II) pincer catalyzed coupling of naphthols with primary allylic alcohols led to the formation of benzo(f)chromanes, whereas the use of secondary alcohols delivered the hydroxyalkyl naphthols. Broad substrate scope and good functional group tolerance are demonstrated. Notably, a high diastereoselectivity is attained on chromanes. Hydroxyalkyl naphthols are synthetically transformed into spiroethers, and dearomative bromination is achieved on chromanes. Mechanistic studies revealed the involvement of tandem reactions, a formal O-H bond activation of allylic alcohols by an active catalyst via amine-amide metal-ligand cooperation provided α-β, unsaturated carbonyl intermediates, which further underwent 1,4 conjugate addition with dearomatized naphthols. One of the crucial intermediates, naphthyl radical, is elucidated by EPR studies and trapped using a radical scavenger. Liberated hydrogen and water molecules are the only byproducts in these transformations.
壬醇的催化脱芳烃化是一项艰巨的任务,但它可以作为与不饱和偶联伙伴构建 C-C 键的有力方法。本文报告了一种简单高效的萘酚与烯丙基醇偶联策略。通过单个 Ru(II) 钳催化萘酚与伯烯丙基醇的偶联,可生成苯并(f)色烷,而使用仲醇则可生成羟基烷基萘酚。这证明了广泛的底物范围和良好的官能团耐受性。值得注意的是,色烷具有很高的非对映选择性。羟基烷基萘酚被合成转化为螺醚,并在色烷上实现了脱芳溴化。机理研究揭示了串联反应的参与:烯丙基醇在活性催化剂的作用下,通过胺酰胺金属配位体的合作,正式的 O-H 键活化提供了 α-β、不饱和羰基中间体,这些中间体进一步与脱芳烃萘酚发生 1,4 共轭加成反应。其中一个关键的中间体--萘基自由基通过 EPR 研究得到了阐明,并使用自由基清除剂将其捕获。释放出的氢和水分子是这些转化过程中唯一的副产物。
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引用次数: 0
Recent Advances in Organocatalytic Asymmetric Synthesis of Bicyclo[3.3.1]nonane Frameworks 双环[3.3.1]壬烷框架的有机催化不对称合成的最新进展
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-16 DOI: 10.1002/adsc.202401158
Rong-Rong Ma, Bo-Yang Liu, Lei Yan, Jun-Bing Lin, Peng-Fei Xu
The bicyclo[3.3.1]nonane ring represents an attractive yet challenging synthetic targets in the field of organic synthesis, especially in a stereocontrolled fashion. Over the past two decades, organocatalysis has emerged as an enabling technology for the facile construction of enantioenriched molecules with remarkably increasing complexity and diversity, and a myriad of chiral architectures containing bicyclo[3.3.1]nonane units were elegantly assembled through organocatalytic asymmetric transformations. This review summarizes recent advancements on this topic (mainly from 2010 to 2023), emphasizing the reaction types such as desymmetrization and cascade reactions of different prochiral starting materials toward various chiral bicyclo[3.3.1]nonanes as well as their aza, oxa and thio derivatives. Meanwhile, the synthetic strategy, reaction mechanism, substrate scope and synthetic applications of these catalytic reactions are also discussed. We hope that this review will motivate further development and application of organocatalytic asymmetric synthesis of bicyclo[3.3.1]nonane frameworks.
双环[3.3.1]壬烷环是有机合成领域极具吸引力但又极具挑战性的合成目标,特别是在立体可控的方式下。在过去的二十年中,有机催化技术的出现使人们能够轻松构建对映体丰富的分子,其复杂性和多样性显著增加,通过有机催化不对称转化,无数含有双环[3.3.1]壬烷单元的手性结构被优雅地组装起来。本综述总结了这一主题的最新进展(主要从 2010 年到 2023 年),强调了不同原手性起始材料向各种手性双环[3.3.1]壬烷及其氮杂、氧杂和硫杂衍生物的去对称化和级联反应等反应类型。同时,还讨论了这些催化反应的合成策略、反应机理、底物范围和合成应用。我们希望这篇综述能推动双环[3.3.1]壬烷框架有机催化不对称合成的进一步发展和应用。
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引用次数: 0
Rh(III)‐Catalyzed C‐H Cyclization of 2‐Arylbenzimidazoles with CF3‐Imidoyl Sulfoxonium Ylides and Further Sc(III)‐Catalyzed Deaminative Hydroxylation Rh(III)-Catalyzed C-H Cyclization of 2-Arylbenzimidazoles with CF3-Imidoyl Sulfoxonium Ylides and Further Sc(III)-Catalyzed Deaminative Hydroxylation
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-11-16 DOI: 10.1002/adsc.202401220
Juting Liao, Ruirui Zhai, Xiaoyang Gao, Hongliang Wu, Dulin Kong, Shuojin Wang, Xun Chen
An efficient Rh(III)‐catalyzed C‐H bond activation/cyclization of 2‐arylbenzimidazoles with CF3‐imidoyl sulfoxonium ylides has been achieved, yielding diverse CF3‐ and amino‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines, which could undergo a deaminative hydroxylation to access CF3‐ and hydroxy‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines under Sc(OTf)3 catalyst. This developed strategy features easily available starting materials, broad substrate scope, ready scalability and high efficiency. Moreover, the antitumor activities of selected products against some human cancer cell lines were also investigated, and the results indicated that several products show the effective antiproliferative activities.
在 Rh(III)催化下,2-芳基苯并咪唑与 CF3-酰亚胺基磺酰亚胺进行了高效的 C-H 键活化/环化反应,得到了多种 CF3-和氨基二取代的 5、6-二氢苯并咪唑并[2,1-a]异喹啉、6-二氢苯并咪唑并[2,1-a]异喹啉,在 Sc(OTf)3 催化剂作用下,这些异喹啉可进行脱氨基羟基化反应,从而得到 CF3-和羟基-二取代的 5,6-二氢苯并咪唑并[2,1-a]异喹啉。所开发的这一策略具有起始材料易得、底物范围广、可随时扩展和效率高等特点。此外,还研究了所选产物对一些人类癌细胞株的抗肿瘤活性,结果表明几种产物具有有效的抗增殖活性。
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引用次数: 0
Front Cover Picture: Dearomative 1,2-(Deutero)Hydrotrifluoromethylation of Chromium-Bound Arenes (Adv. Synth. Catal. 20/2024) 封面图片:铬结合烯的1,2-(脱氘代)氢三氟甲基化反应(Adv.)
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-10-25 DOI: 10.1002/adsc.202401219
Cheng-Jie Wu, Xu Jiang, Jia-Yi Qiu, Ming-Yang Wang, Wei Li

The front cover presents the conversion of simple benzene derivatives into high-value trifluoromethyl-containing cyclohexadienes. The background shows the gate of Qiushi Academy, which is the former site of Zhejiang University. With a chromium-mediated η6-coordination strategy to activate inert arene π-bonds, both dearomative 1,2-hydrotrifluoromethylation and dearomative 1,2-deuterotrifluoromethylation were readily realized. More details can be found in the Communication by Wei Li and co-workers (C.-J. Wu, X. Jiang, J.-Y. Qiu, M.-Y. Wang, W. Li, Adv. Synth. Catal. 2024, 366, 4195–4199; DOI: 10.1002/adsc.202400718)

封面介绍了将简单苯衍生物转化为高价值的含三氟甲基环己二烯的过程。背景是浙江大学旧址求是书院的大门。通过铬介导的η6配位策略激活惰性炔π键,脱芳1,2-氢三氟甲基化反应和脱芳1,2-氚三氟甲基化反应都很容易实现。更多详情可参见李伟及其合作者的通讯(C.-J. Wu, X. Jiang, J.-Y.Qiu, M.-Y. Wang, W. Li, Adv.W. Li, Adv. Synth.Catal.2024, 366, 4195-4199; DOI: 10.1002/adsc.202400718)
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引用次数: 0
The Current State of the Art of Dearomatization Chemistry 脱芳烃化学的技术现状
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-10-25 DOI: 10.1002/adsc.202401218
David Sarlah, Shu-Li You

在小型有机分子中,芳香族化合物被认为是最丰富、用途最广的构件之一,目前每年的产量达一亿吨。此外,由于其固有的共振稳定性,近两个世纪以来,芳香族化合物一直吸引着科学家的目光,同时也为合成化学家带来了无尽的灵感。烯的化学性质自成一类,因为只有这类化合物才具有许多独特的反应活性。脱芳烃反应就是其中一种特征性转化--这种反应可以克服芳香稳定作用,将烯烃转化为饱和、非芳香化合物。从历史上看,这类转化仅限于脱芳烃氢化、溶解金属还原(桦木反应)和苯酚氧化;然而,在过去的几十年中,该领域的新型脱芳烃策略呈指数级增长,并取得了根本性进展。由于医药和天然产品化学迫切需要生产具有密集功能性、饱和度(sp3 含量)不断提高以及不同螺环和多环结构的分子,脱芳烃反应已成为合成化学和分子科学前沿领域提供多种解决方案的平台。结合催化、光化学、杂环化学、电化学和生物催化等领域的进步和最新反应范式,产生了大量脱芳烃方法,极大地扩展了从简单烷烃中获得构件的范围和复杂性。这些方法包括在脱芳烃过程中采用不对称催化策略的对映体选择性变体。我们感谢作者们的宝贵贡献,这些贡献展示了这些转化过程如何提供独特的分子断开和产物,提供了有机合成中最快速的复杂性生成策略之一,并将在未来的岁月中继续启发我们。
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引用次数: 0
Front Cover Picture: Exploring Ferrocenyl Imine-Phosphane Complexes in Gold(I) Redox Switchable Catalysis and the Role of the “Magic Blue” Oxidant (Adv. Synth. Catal. 18/2024) 探索二茂铁酰亚胺-膦烷配合物在金(I)氧化还原可转换催化作用中的作用以及 "魔蓝 "氧化剂的作用。
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-09-18 DOI: 10.1002/adsc.202400921
Juan Carlos Pérez-Sánchez, Raquel P. Herrera, M. Concepción Gimeno

The front cover illustrates the dual role of the “Magic Blue” molecule. Set in an enchanting forest, a whimsical wizard conjures two gold complexes in a magical cauldron full of “Magic Blue”. The compounds react via chloride abstraction for the [AuCl(JohnPhos)] catalyst and one-electron oxidation for the ferrocenyl imine-phosphane catalyst. Fairies are depicted pulling a chloride atom and an electron, respectively, showcasing the dynamic nature that “Magic Blue” oxidant can adopt depending on the molecule it reacts with. Details can be found in Research Article by Pérez-Sánchez, Herrera, and Gimeno (J. C. Pérez-Sánchez, R. P. Herrera, M. C. Gimeno, Adv. Synth. Catal. 2024, 366, 3697–3924; DOI: 10.1002/adsc.202400593)

封面展示了 "魔法蓝 "分子的双重作用。在一片迷人的森林中,一位奇思妙想的魔法师在一个装满 "魔法蓝 "的神奇大锅中变幻出两种金络合物。在[AuCl(JohnPhos)]催化剂中,化合物通过氯化物抽取反应,在二茂铁酰亚胺-膦催化剂中,化合物通过单电子氧化反应。图中的仙女分别拉动一个氯原子和一个电子,展示了 "魔蓝 "氧化剂可根据与之反应的分子的不同而具有的动态性质。详情请见佩雷斯-桑切斯、埃雷拉和吉梅诺的研究文章(J. C. Pérez-Sánchez, Herrera, and Gimeno)。Pérez-Sánchez, R. P.Herrera, M. C.Gimeno, Adv.Catal.2024, 366, 3697-3924; DOI: 10.1002/adsc.202400593)
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引用次数: 0
Advances in α‐Hydroxylation of β‐Dicarbonyl Compounds β-二羰基化合物的α-羟基化研究进展
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2024-09-17 DOI: 10.1002/adsc.202400627
Shuai Peng , Fangyao Su , Shuting Yin , Baoguo Sun , Hongyu Tian , Sen Liang
The α‐hydroxy‐β‐dicarbonyl motif is essential in many biologically active compounds, sparking significant interest in their synthesis. This review comprehensively examines the advancements in the α‐hydroxylation of β‐dicarbonyl compounds, systematically categorizing the methods based on the types of oxidants employed and highlighting advances in asymmetric α‐hydroxylation. It evaluates the substrate scope, advantages, and disadvantages of each approach, summarizing the possible intermediates involved and the types of reaction mechanisms.
在许多具有生物活性的化合物中,α-羟基-β-二羰基基团是必不可少的,这引发了人们对其合成的极大兴趣。本综述全面研究了 α- 羟基-β-二羰基化合物的合成进展,根据所使用的氧化剂类型对方法进行了系统分类,并重点介绍了不对称 α- 羟基合成的进展。报告评估了每种方法的底物范围、优缺点,总结了可能涉及的中间产物和反应机制类型。
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引用次数: 0
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Advanced Synthesis & Catalysis
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