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Activating Methanol for Chemoselective Transfer Hydrogenation of Chalcones Using an SNS-Ruthenium Complex 利用 SNS-Ruthenium 复合物活化甲醇以进行查耳酮的化学选择性转移加氢反应
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-09-09 DOI: 10.1055/a-2384-6441
Kailash Mohar, Hirak Jyoti Phukan, Avijit Mondal, Kaushik Soni, Dipankar Srimani

Methanol is gaining popularity as a transfer-hydrogenating agent in catalytic reduction reactions because of its bulk-scale production and inexpensive nature. Current research interests include the utilization of methanol as a safe and sustainable hydrogen source for chemical synthesis and drug development. In particular, the chemoselective reduction of α,β-unsaturated ketones is of great interest because of their prevalence in many natural products. We investigated the potential application of acridine-derived SNS-Ru pincer complexes in methanol activation for chemoselective reduction of chalcones. Our developed catalytic system showed broad substrate tolerance, including substrates containing reducible functional groups. Control experiments and postsynthetic applications are also highlighted.

甲醇作为催化还原反应中的转移加氢剂,因其批量生产和价格低廉而越来越受欢迎。目前的研究兴趣包括将甲醇作为一种安全、可持续的氢源用于化学合成和药物开发。特别是,α、β-不饱和酮的化学选择性还原反应引起了极大的兴趣,因为它们在许多天然产品中普遍存在。我们研究了吖啶衍生的 SNS-Ru 钳子配合物在甲醇活化中化学选择性还原查耳酮的潜在应用。我们开发的催化系统对底物具有广泛的耐受性,包括含有可还原官能团的底物。此外,还重点介绍了对照实验和合成后的应用。
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引用次数: 0
Nickel-Catalyzed Radical Hydroalkylative Dearomatization of Indoles with Alkyl Bromides 镍催化的吲哚与烷基溴的自由基氢烷基化反应
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-09-04 DOI: 10.1055/a-2382-0292
Hao-Tian Dai, Xu-Lun Huang, Yuan-Zheng Cheng, Shu-Li You

Dearomatization of indole derivatives offers a straightforward approach to accessing the indoline framework. However, highly efficient dearomatization of indoles bearing electron-deficient groups remains underdeveloped. Herein, a nickel-catalyzed intermolecular hydroalkylative dearomatization reaction of indoles with simple alkyl bromides through a single-electron-transfer process is reported. A wide variety of indole derivatives bearing various functional groups were compatible with this protocol and reacted with primary, secondary, or tertiary alkyl bromides to afford a series of indolines in good yields (up to 82%) and with excellent diastereoselectivity (up to >20:1). Notably, a nickel-mediated hydrogen-atom-transfer process was observed when terminal alkyl bromides were employed as the radical precursors, which resulted in branched products.

吲哚衍生物的脱芳烃化为获得吲哚啉框架提供了一种直接的方法。然而,对含有缺电子基团的吲哚进行高效脱芳烃反应的技术仍未得到充分发展。本文报告了一种镍催化的分子间氢烷基脱芳烃反应,通过单电子转移过程将吲哚与简单的溴化烷基进行反应。各种带有不同官能团的吲哚衍生物都能与该方案相容,并能与伯基、仲基或叔基烷基溴化物反应,以良好的收率(高达 82%)和优异的非对映选择性(高达 >20:1)得到一系列吲哚类化合物。值得注意的是,当使用末端烷基溴作为自由基前体时,观察到了镍介导的氢原子转移过程,从而得到了支化产物。
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引用次数: 0
Iron(III) Triflate and γ-Cyclodextrin-Catalyzed Hydroarylation of Alkenes with 1-Naphthols and 2-Naphthols 三氟化铁和 γ-环糊精催化烯烃与 1-萘酚和 2-萘酚的加氢反应
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-09-04 DOI: 10.1055/a-2382-3010
Meng-Xue Hu, Peng Chen, Le-Wei Miao, Jianghuan Shi, Yi-Jun Jiang

A Fe(OTf)3 and γ-cyclodextrin-catalyzed hydroarylation of alkenes with 1-naphthols or 2-naphthols is demonstrated. This efficient and general method delivers a wide range of benzylic naphthols from readily available starting materials with high chemo- and regioselectivity in up to 99% yield, with no need for a strong base or additive.

展示了一种由 Fe(OTf)3 和 γ-环糊精催化的 1-萘酚或 2-萘酚与烯烃的加氢反应。这种高效而通用的方法可从易于获得的起始材料中得到多种苄基萘酚,具有很高的化学和区域选择性,收率高达 99%,且无需强碱或添加剂。
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引用次数: 0
Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State 具有三重基态的手性π-共轭双螺旋氨酰基二旋体
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-09-02 DOI: 10.1055/a-2379-9406
Haoxin Guo, Andrzej Rajca

We describe effective development of the highly diastereoselective synthesis of double helical tetraamine 2-H2-C2 and propose a mechanism for its formation. The resolution of 2-H2-C2 is facilitated by a high racemization barrier of 43 kcal mol–1 and it is implemented via either a chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation of the first high-spin neutral diradical, with spin density delocalized within an enantiomeric double helical π-system. The presence of two effective 3-electron C–N bonds in the diradical leads to: (1) the triplet (S = 1) high-spin ground state with a singlet-triplet energy gap of 0.4 kcal mol–1 and (2) the long half-life of up to 6 days in 2-MeTHF at room temperature. The diradical possesses a racemization barrier of at least 26 kcal mol–1 in 2-MeTHF at 293 K and chiroptical properties, with an absorption anisotropy factor |g| ≈ 0.005 at 548 nm. These unique magnetic and optical properties of our diradical form the basis for the development of next-generation spintronic devices.

1 Introduction

2 Synthesis and Resolution of the C2-Symmetric Double Helical Tetraamine 2-H2-C2

3 Synthesis and Characterization of Neutral High-Spin Aminyl Diradical 22•-C2

4 Conclusion

我们介绍了高非对映选择性合成双螺旋四胺 2-H2-C2 的有效方法,并提出了其形成机理。43 kcal mol-1 的高消旋化阻垒促进了 2-H2-C2 的解析,并通过手性辅助剂或制备型超临界流体色谱法实现了解析。这样就能制备出第一种高自旋中性二维化合物,其自旋密度分散在对映体双螺旋 π 系统中。该二元对映体中存在两个有效的 3 电子 C-N 键,这导致:(1) 三重(S = 1)高自旋基态,单重-三重能隙为 0.4 kcal mol-1;(2) 在室温下于 2-MeTHF 中的半衰期长达 6 天。在 2-MeTHF 293 K 的条件下,该二元化合物的消旋化势垒至少为 26 kcal mol-1,并具有各向异性,在 548 nm 波长处的吸收各向异性系数 |g |≈ 0.005。我们的二维化合物所具有的这些独特的磁学和光学特性为开发下一代自旋电子器件奠定了基础。1 引言 2 C2 对称双螺旋四胺 2-H2-C2 的合成与解析 3 中性高旋氨酰二拉锥 22-C2 的合成与表征 4 结论
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引用次数: 0
Dehydrosilylation of Alcohols Using Gold Nanoparticles Deposited on Citric Acid Modified Fibrillated Cellulose 使用沉积在柠檬酸改性纤维素上的金纳米粒子对醇进行脱氢硅烷化处理
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-09-02 DOI: 10.1055/a-2379-9191
Butsaratip Suwattananuruk, Yuta Uetake, Hidehiro Sakurai

The development of an effective catalytic system for the dehydrogenative coupling of hydrosilanes with alcohols remains an ongoing challenge, particularly for alcohol protection applications. In this study, we report the development and optimization of a highly efficient gold catalyst supported on fibrillated cellulose modified with citric acid. The catalyst exhibited remarkable catalytic activity under mild conditions with 0.01–0.05 mol% of Au loading, facilitating the formation of silyl ethers with excellent yield. Notably, our catalytic system overcomes the need for excess alcohol, typically required in such reactions, making it highly practical for alcohol protection applications. This work represents a significant advancement in the field of dehydrosilylation catalysis, offering a sustainable, efficient, and environmentally friendly approach for the synthesis of functional silanol-based materials and alcohol protection applications. The scope of substrates and the utility of the catalyst have been thoroughly studied.

为氢硅烷与醇类的脱氢偶联开发有效的催化系统仍然是一个持续的挑战,尤其是在酒精保护应用方面。在本研究中,我们报告了一种高效金催化剂的开发和优化,该催化剂以柠檬酸修饰的纤维化纤维素为支撑。在金负载量为 0.01-0.05 摩尔%的温和条件下,该催化剂表现出显著的催化活性,促进了硅烷醚的生成,且收率极高。值得注意的是,我们的催化系统克服了此类反应中通常需要的过量酒精,使其在酒精保护应用中非常实用。这项工作代表了脱氢硅烷化催化领域的重大进展,为硅醇基功能材料的合成和酒精保护应用提供了一种可持续、高效和环保的方法。我们对底物的范围和催化剂的实用性进行了深入研究。
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引用次数: 0
Temperature-Controlled Synthesis of Thiophenol-VBXs from EBXs and Thiophenols 由 EBX 和噻吩酚在温控下合成噻吩酚-VBXs
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-08-30 DOI: 10.1055/a-2377-0118
Jun Li, Chuang Zhou, Lian-Mei Chen, Xing-Yu Chen, Xiao-Qiang Guo, Tai-Ran Kang

Vinylbenziodoxolones (VBXs) are important electrophilic alkene synthons. However, the synthesis of cis-thiophenol-VBX reagents from ethynylbenziodoxolones (EBXs) and thiophenols remains challenging. Herein, we explore an efficient method for the synthesis of cis-thiophenol-VBXs in excellent yield with excellent regio- and stereoselectivities from EBXs and thiophenols under temperature-controlled conditions.

乙烯基苯并二恶酮(VBX)是重要的亲电烯合成物。然而,从乙炔基苯并二恶唑酮(EBXs)和噻吩酚合成顺式噻吩酚-VBX 试剂仍然具有挑战性。在此,我们探索了一种在温控条件下从 EBXs 和噻吩酚合成顺式噻吩酚-VBX 的高效方法,该方法具有极佳的产率和良好的区域及立体选择性。
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引用次数: 0
Advances in the Intermolecular Asymmetric Allylic Functionalization of Unreactive Acyclic Alkenes 非活性无环烯的分子间不对称烯丙基官能团化研究进展
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-08-29 DOI: 10.1055/a-2375-7634
Mingyue Zhang, Mengmeng Zhang, Changsheng Li, Wenyang Wang, Guohui Shi, Shipeng Luo, Liang-An Chen, Qiang Dai

Allylic C(sp3)–H functionalized architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials, but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry. Accordingly, various strategies to access allylic functionalized alkenes in a stereoselective manner have been developed. However, chemo-, regio- and stereoselective intermolecular asymmetric allylic functionalization (AAF) of unreactive acyclic alkene (UAA) from readily available materials, representing a highly atom- and step-economic approach toward the generation of structural complexity, remains elusive and challenging. Herein, we review all intermolecular asymmetric catalyzed methods, with emphasis on the construction of chiral allylic units by activation of allylic C–H bonds of UAAs. Our analysis serves to document the considerable and rapid progress within the field, while also highlighting the limitations of current methods.

1 Introduction

2 Asymmetric Allylic Oxygenation

3 Asymmetric Allylic Amination

4 Asymmetric Allylic Carbonization

5 Asymmetric Allylic Sulfuration

6 Conclusion and Outlook

烯丙基 C(sp3)-H 功能化结构不仅广泛存在于天然产物、药物和功能有机材料中,而且还是合成化学中提供重要功能化分子的多功能构建模块。因此,以立体选择性方式获得烯丙基功能化烯烃的各种策略已经开发出来。然而,从容易获得的材料中对无反应无环烯(UTA)进行化学、区域和立体选择性分子间不对称烯丙基官能化(AAF),作为一种高度原子和步骤经济的方法来生成结构复杂的烯烃,仍然是一个难以捉摸和具有挑战性的问题。在此,我们回顾了所有分子间不对称催化方法,重点是通过活化 UAA 的烯丙基 C-H 键来构建手性烯丙基单元。我们的分析记录了该领域取得的巨大而迅速的进展,同时也强调了当前方法的局限性。1 引言 2 不对称烯丙基氧化反应 3 不对称烯丙基胺化反应 4 不对称烯丙基碳化反应 5 不对称烯丙基硫化反应 6 结论与展望
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引用次数: 0
Direct Synthesis of N-Substituted Phosphinecarboxamides from [TBA][P(SiCl3)2] and Isonitriles 由 [TBA][P(SiCl3)2]和异腈直接合成 N-取代的膦甲酰胺
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-08-29 DOI: 10.1055/s-0043-1775388
Bo Yang, Xin Wang, Yao Chai, Wen-Bo Xu, Ya-Ling Tian, Yong-Jun Ma, Anwar I. Alduma, Xin-Rui Cao, Xi-Cun Wang, Dong-Ping Chen, Zheng-Jun Quan

In this investigation, N-substituted phosphinecarboxamides were produced through the reaction of [TBA][P(SiCl3)2] with isonitriles. This method capitalizes on the flexibility of isonitriles as a source of both nitrogen and carbonyl groups, offering a novel route to the generation of PH2-type compounds. This approach is characterized by rapid reaction times, simple procedural requirements, compatibility with a diverse array of substrates, and the conversion of [TBA][P(SiCl3)2] into organic phosphorus compounds. Additionally, we systematically studied the reaction mechanism of isonitrile with [TBA][P(SiCl3)2] through controlled experiments and density functional theory (DFT) calculations.

在这项研究中,[TBA][P(SiCl3)2] 与异腈反应生成了 N-取代的膦甲酰胺。这种方法利用了异腈作为氮和羰基来源的灵活性,为生成 PH2- 型化合物提供了一条新途径。这种方法的特点是反应时间快、程序要求简单、与多种底物兼容,并能将 [TBA][P(SiCl3)2] 转化为有机磷化合物。此外,我们还通过对照实验和密度泛函理论 (DFT) 计算系统地研究了异腈与 [TBA][P(SiCl3)2]的反应机理。
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引用次数: 0
Synthesis of Chiral L2/Z-Type Ligands Featuring a Bisoxazoline Framework and Their Application to Palladium-Catalyzed Asymmetric Allylic Alkylation 具有双噁唑啉框架的手性 L2/Z 型配体的合成及其在钯催化不对称烯丙基烷基化中的应用
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-08-26 DOI: 10.1055/a-2377-0844
Hikaru Takahashi, Takashi Shibata, Daisuke Naito, Ryo Murakami, Fuyuhiko Inagaki

Chiral L2/Z*-type ligands featuring a bisoxazoline framework have been successfully synthesized and applied in asymmetric allylic alkylation. These ligands, designed based on an oxazoline skeleton and derived from chiral amino acid derivatives, incorporate antimony and bismuth as Z-type ligands. Ligands with bulky, electron-withdrawing groups on antimony and bismuth showed enhanced catalytic performance. This research highlights the potential of these novel chiral L2/Z*-type ligands to improve asymmetric catalysis.

以双噁唑啉骨架为特征的手性 L2/Z* 型配体已被成功合成并应用于不对称烯丙基烷基化反应。这些配体以噁唑啉骨架为基础设计,源自手性氨基酸衍生物,并加入了锑和铋作为 Z 型配体。在锑和铋上带有笨重的抽电子基团的配体显示出更强的催化性能。这项研究凸显了这些新型手性 L2/Z* 型配体在改善不对称催化方面的潜力。
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引用次数: 0
Introduction of Fluorinated Groups via Photoredox-Catalyzed C–H Functionalization of (Hetero-)Arenes 通过光氧化催化(杂)烯的 C-H 功能化引入氟化基团
IF 2 4区 化学 Q3 CHEMISTRY, ORGANIC Pub Date : 2024-08-23 DOI: 10.1055/a-2377-0629
Jonas F. Goebel, Sourav Manna, Pierpaolo Satta, Nikolaos V. Tzouras, Lukas J. Gooßen

In recent years, there have been increasing efforts in the development of methodologies for incorporating fluorine-containing functional groups into organic scaffolds. Modern techniques have made fluorinated molecules more accessible than ever before, but many fluorination reactions still have limitations in their generality, predictability, sustainability, and cost-effectiveness. The methodological progress has a significant impact on drug discovery and materials science research. Photoredox catalysis has enabled the discovery of effective methods, providing access to druglike molecules. Photochemical methods paired with C–H functionalization provide powerful tools for property-driven research. Herein, we examine recent developments at the interface of photoredox catalysis and C–H functionalization.

1 Introduction

2 Fluorinations

3 Fluoroalkylations

4 Fluoroalkoxylations

5 Conclusion

近年来,人们越来越努力地开发将含氟官能团纳入有机支架的方法。现代技术使含氟分子比以往任何时候都更容易获得,但许多氟化反应在通用性、可预测性、可持续性和成本效益方面仍有局限。方法上的进步对药物发现和材料科学研究产生了重大影响。光氧化催化技术使人们能够发现有效的方法,从而获得类似药物的分子。光化学方法与 C-H 功能化相配合,为性质驱动型研究提供了强大的工具。在此,我们将探讨光氧化催化和 C-H 功能化界面的最新进展。1 引言 2 氟化反应 3 氟烷基化反应 4 氟烷氧基化反应 5 结论
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