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Brønsted Acid-Mediated Selective α-Alkenylation of 3,4-Dihydropyrans 布氏硬度酸介导的 3,4-二氢吡喃的选择性 α 烯化反应
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00541d
Nan Chen, Chaokun Li, Shangteng Liao, Jinglong Chen, Xingxing Ma, Qiuling Song
A protocol for the synthesis of α-mono/disubstituted tetrahydropyrans (THPs) with vinyl cyclic ethers and potassium trifluorob-orates was achieved in the presence of Brønsted acid and Lewis acid under mild reaction conditions. The oxonium ions intermediates, produced from various readily available vinyl cyclic ethers, were attacked by the nucleophile to form the desired α-alkenylation products. This strategy could be an alternative approach to modify a series of modules that are of broad utility in natural products and fine chemicals.
在温和的反应条件下,在布氏酸和路易斯酸的存在下,用乙烯基环醚和三氟硼酸钾合成了α-单/二取代的四氢吡喃(THPs)。由各种现成的乙烯基环醚生成的羰基离子中间体在亲核剂的作用下形成了所需的α-烯基化产物。这种策略可以作为一种替代方法,对天然产品和精细化学品中具有广泛用途的一系列模块进行改性。
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引用次数: 0
Direct C−H Sulfonylation of Hydrazones Involving the Insertion of SO2 涉及二氧化硫插入的肼的直接 C-H 磺化反应
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00835a
Mengzhao Yu, Shuizhen Lin, Shuoshuo Zhang, Xinkui Lin, Xiaolei Huang
A three-component reaction of aldehyde-derived hydrazones with DABSO and aryldiazonium tetrafluoroborates is described. By using organic DABSO as the source of SO2, this straightforward sulfonylation tactic provides an elegant access to (E)-sufonylated hydrazones in moderate to excellent yields. Moreover, the sulfonylation of hydrazones can also be achieved under photocatalyzed conditions by using sulfonyl chlorides as the active sulfonylating reagents.
本文介绍了醛基肼与 DABSO 和芳基偶氮四氟硼酸盐的三组分反应。通过使用有机 DABSO 作为 SO2 的来源,这种直接的磺酰化方法为中等至极好收率的 (E)-sufonylated 肼酮提供了一个优雅的途径。此外,利用磺酰氯作为活性磺化试剂,还可以在光催化条件下实现肼的磺化反应。
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引用次数: 0
Synthesis of Axially Chiral Biaryls via Pd(II)-Catalysed Direct C(sp2)-H Arylation 通过 Pd(II)-Catalysed Direct C(sp2)-H Arylation 合成轴向手性双酯
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00958d
Diksha Parmar, Rohit Kumar, Sarthi ., Akhilesh Kumar Sharma, Upendra Sharma
A concise protocol for the construction of axially chiral biaryls via Pd-catalyzed direct C-H arylation of 1-arylisoquinoline N-oxides through kinetic resolution using commercially available, cost-effective, and bench-stable chiral mono-protected amino acid have been uncovered. The high conformational stability of the axially chiral products in different solvents and at high temperatures, as observed from the experimental studies and DFT calculations, shows their excellent stability.
通过使用市场上可买到的、具有成本效益和工作台稳定性的手性单保护氨基酸进行动力学解析,发现了一种通过 Pd 催化 1-芳基异喹啉 N-氧化物的直接 C-H 芳基化反应构建轴向手性双芳基化合物的简明方案。通过实验研究和 DFT 计算观察到,轴向手性产物在不同溶剂和高温条件下具有很高的构象稳定性,这表明它们具有极佳的稳定性。
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引用次数: 0
Elucidating the mechanism and origin of diastereoselectivity in scandium-catalyzed β-C(sp3)-H activation and transformation of an aliphatic aldimine 阐明钪催化脂肪族醛亚胺的 β-C(sp3)-H 活化和非对映选择性的机理和来源
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00567h
Yiran Zhang, Yang Wang
The elucidation of exact reaction mechanisms, especially for the purpose of determining the origin of regio-and diastereo-selectivity, is essential for furthering the development of substituent divergent reactions. In this study, density functional theory calculations were carried out to elucidate the mechanism and thereby, the origin of regio- and diastereo-selectivity, of the divergent [3+2] annulation of an aldimine with alkenes catalyzed by the rare-earth metal scandium (Sc). The reaction mechanism was found to consist of the generation of active species, C(sp3)-H activation, alkene insertion, ring-closure, and protonation processes. The alkene insertion process was found to determine the regio- and diastereoselectivity of the reaction. The main role of the amine is to lower the positive charge of the Sc atom, thereby weakening and cleaving the Sc-C(sp3) bond, before forming an Sc-C(sp2) bond forms during the alkene insertion process. These results provide valuable insights into the reactions catalyzed by rare-earth metals.
阐明确切的反应机理,特别是为了确定区域和非对映选择性的来源,对于进一步发展取代基发散反应至关重要。本研究通过密度泛函理论计算,阐明了稀土金属钪(Sc)催化的醛亚胺与烯烃的[3+2]环化分歧反应的机理,从而确定了区域和非对映选择性的来源。研究发现,反应机理包括活性物种生成、C(sp3)-H 活化、烯插入、环闭合和质子化过程。发现烯插入过程决定了反应的区域和非对映选择性。胺的主要作用是降低 Sc 原子的正电荷,从而削弱和裂解 Sc-C(sp3)键,然后在烯插入过程中形成 Sc-C(sp2)键。这些结果为了解稀土金属催化的反应提供了宝贵的见解。
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引用次数: 0
Access to Chiral Sulfones with An All-Carbon Quaternary Stereocenter from Sulfur Dioxide 利用二氧化硫获得具有全碳季态立体中心的手性砜
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00671b
Chunxi Huang, Xuemei Zhang, Liping Luo, Xiuwen Jia, Jian Liao, Zhong Lian
Sulfur dioxide (SO2), as an atmospheric pollutant, has been increasingly attracting the interest of scientists regarding its chemical utilization. Vicinal sulfonyl-functionalization of alkenes through SO2 insertion offers an innovative method to introduce both sulfonyl and other functional groups into a single molecule. This approach boosts compound diversity while eliminating the need for multi-step operations. On the other hand, asymmetric construction of quaternary all-carbon stereocenters remains a persistent synthetic challenge. In particular, methods for the synthesis of chiral sulfones bearing an all-carbon quaternary stereocenter are rare. Herein, we present a copper-catalyzed vicinal cyano-arylsulfonylation of acrylamides via the insertion of sulfur dioxide (SO2), providing an easy access to achieve this goal with minimally functionalized starting materials. The reaction proceeds under mild conditions through a verified single-electron-transfer (SET) mechanism with excellent enantioselectivity (mostly >99% ee), good functional group tolerance, and a broad substrate scope (>50 examples). Notably, this four-component reaction is applicable to the direct chiral functionalization of amino acid and peptide derivatives.
二氧化硫(SO2)作为一种大气污染物,越来越引起科学家们对其化学利用的兴趣。通过插入二氧化硫对烯进行侧向磺酰基官能化提供了一种创新方法,可在单个分子中同时引入磺酰基和其他官能团。这种方法提高了化合物的多样性,同时消除了多步骤操作的需要。另一方面,四元全碳立体中心的不对称构建仍然是一个长期存在的合成难题。尤其是合成带有全碳季立体中心的手性砜的方法非常罕见。在本文中,我们介绍了一种铜催化的丙烯酰胺代氰芳磺酰化反应,该反应通过二氧化硫(SO2)的插入,为实现这一目标提供了一条简便的途径,而且起始材料的官能度极低。该反应在温和的条件下通过验证的单电子转移(SET)机理进行,具有极佳的对映选择性(大多为 99%ee)、良好的官能团耐受性和广泛的底物范围(50 个实例)。值得注意的是,这种四组分反应适用于氨基酸和肽衍生物的直接手性官能化。
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引用次数: 0
Lewis acid-catalyzed phosphinoylation and halogenation of α,β-unsaturated ketones: Access to γ-halo allylic phosphonates 路易斯酸催化的 α、β-不饱和酮的膦酰化和卤化反应:获得γ-卤代烯丙基膦酸盐
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-17 DOI: 10.1039/d4qo00748d
Xiao-Hong Wei, Ya-Wen Xue, Chun-Yuan Bai, Xuan Liu, Xiao-Hong Wang, Yanbin Wang, Qiong Su
A Lewis acid-catalyzed phosphinoylation and halogenation of α,β-unsaturated ketones to synthesize γ-halo allylic phosphonates is described. This transformation consists of a phospha-Michael addition, unimolecular elimination dehydration cascade reaction for the introduction of versatile groups (−P(O)R3R4 and −X) in the resulting γ-substituent allylic phosphonates with high regio- and stereoselectively.
本研究描述了一种路易斯酸催化的 α、β-不饱和酮的膦酰化和卤化反应,以合成 γ-卤代烯丙基膦酸盐。这一转化过程包括一个膦-迈克尔加成、单分子消去脱水级联反应,在生成的γ-取代基烯丙基膦酸盐中引入多功能基团(-P(O)R3R4 和 -X),并具有高度的区域和立体选择性。
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引用次数: 0
A Domino [3+2] Cycloaddition/Deamination/Imine Hydrolysis Reaction of Cyclopropyl Spirooxindoles with Thiourea for Access to Spiro-γ-thiolactone oxindoles 环丙基螺吲哚与硫脲的多米诺[3+2]环加成/脱氨/亚胺水解反应,以获得螺-γ-硫内酯吲哚肟
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-15 DOI: 10.1039/d4qo00833b
Hai-Ting Wang, Xiao-Lin Wen, Xiao-Lin Xu, Dong-Chao Wang, Hai-Ming Guo
An efficient method for a domino [3+2] cycloaddition/deamination/imine hydrolysis reaction of D-A cyclopropane with inexpensive thiourea catalyzed by Lu(OTf)3 has been developed. A series of spiro-γ-thiolactone oxidized indole compounds with potential biological activity were obtained up to 98% yields. Experiments to investigate the mechanism showed that γ-thiolactone products were from the hydrolysis of the imine intermediate. In addition, the asymmetric catalytic synthesis of D-A cyclopropane and thiourea has been successfully developed to afford the spiro-γ-thiolactone compounds in good enantioselectivity (up to 98% ee). The utility of this method was showcased by the facile transformation and biological activity of products.
在 Lu(OTf)3 催化下,开发了一种高效的 D-A 环丙烷与廉价硫脲的多米诺[3+2]环加成/脱氨/亚胺水解反应方法。获得了一系列具有潜在生物活性的螺-γ-硫内酯氧化吲哚化合物,收率高达 98%。机理研究实验表明,γ-硫内酯产物来自亚胺中间体的水解。此外,还成功开发了 D-A 环丙烷和硫脲的不对称催化合成方法,以良好的对映选择性(高达 98% ee)得到螺-γ-硫内酯化合物。产品的易转化性和生物活性证明了该方法的实用性。
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引用次数: 0
Electroreduction Strategy: A Sustainable Tool for Generation of Aryl Radicals 电还原策略:生成芳基自由基的可持续工具
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-15 DOI: 10.1039/d4qo00846d
Xiao-Qing Xie, Wei Zhou, Ruchun Yang, Xian-Rong Song, Mu-Jia Luo, Qiang Xiao
Aryl radicals are important and versatile active intermediates in synthetic chemistry, and the chemical conversions involved are regarded as perfect complements to the transition-metal-catalyzed arylation reactions. The formation of aryl radicals is mainly achieved through reductive systems. Electrocatalysis has a safe and controllable potential range that can easily attain a reduction potential beyond the range of chemical reductants and excited photocatalysts, offering a synthetically attractive and environmentally friendly alternative for the production of aryl radicals. Remarkable achievements in the electrochemical functionalization of aryl radicals have been reported. This review primarily focuses on the generation of aryl radicals via electroreduction strategy, and systematically elaborates on synthetic applications, scope, and limitations of the substrates. A full spectrum of aryl radical precursors applied in the electroreduction strategy is reviewed, including aryl halides, aryl diazonium salts, arylazo sulfones, aryl amines, nitroarenes, aryl quaternary ammonium salts, aryl triflates, and aryl thianthrenium salts.
芳基自由基是合成化学中重要的多功能活性中间体,其化学转化过程被视为过渡金属催化芳基化反应的完美补充。芳基自由基的形成主要是通过还原体系实现的。电催化具有安全可控的电位范围,可以轻松达到超出化学还原剂和激发光催化剂范围的还原电位,为生产芳基自由基提供了一种具有合成吸引力且环保的替代方法。据报道,芳基自由基的电化学功能化取得了显著成就。本综述主要关注通过电还原策略生成芳基自由基,并系统阐述了基质的合成应用、范围和局限性。综述了应用于电还原策略的各种芳基自由基前体,包括芳基卤化物、芳基重氮盐、芳基偶氮砜、芳基胺、硝基烯烃、芳基季铵盐、芳基三氟酸盐和芳基噻吩盐。
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引用次数: 0
Ir/Co Dual Catalyzed Hydroacylation of Electron-Deficient Alkenes Overcoming Redox Potential Limitations 克服氧化还原电位限制的 Ir/Co 双催化缺电子烯烃加氢反应
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-14 DOI: 10.1039/d4qo00778f
Yi Zhou, Yong Qin He, Xia Nie, Lin Lu, Xian-Rong Song, Zhao-Zhao Zhou, Wan-Fa Tian, Qiang Xiao
An unexcepted Ir/Co dual catalytic hydroacylation of electron-deficient alkenes overcoming redox potential limitations is reported. In this protocol, Co(I) species are generated via photoreduction using Ir[dF(CF3)ppy]2dtbbpy, which excited state has an oxidative potential (Eox = -0.89 V vs SCE) close to or lower than the reduction potential of several effective salen-Co(II) catalysts (Co-1~Co-5: ECo(II)/Co(I) = -0.80 to -1.36 V vs SCE). The nucleophilic Co(I) species catalyzes the fragmentation of carboxylic anhydrides to release acyl radical, which were subsequently captured by electron-deficient alkenes.
本研究报告介绍了一种克服氧化还原电位限制的未接受过的 Ir/Co 双催化缺电子烯烃加氢酰化反应。在该方案中,Co(I) 物种是通过使用 Ir[dF(CF3)ppy]2dtbbpy 进行光反应生成的,其激发态的氧化电位(Eox = -0.89 V vs SCE)接近或低于几种有效的沙林-Co(II) 催化剂的还原电位(Co-1~Co-5:ECo(II)/Co(I) = -0.80 至 -1.36 V vs SCE)。亲核的 Co(I) 物种催化羧酸酐碎裂,释放出酰基,随后被缺电子的烯捕获。
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引用次数: 0
Copper/Ruthenium Relay Catalysis for Stereodivergent Construction of 1,4-Nonadjacent Stereocenters: Mechanistic Investigation Using DFT Calculations 铜/钌接力催化 1,4-不相邻立体中心的立体异构:利用 DFT 计算进行机理研究
IF 5.4 1区 化学 Q1 Chemistry Pub Date : 2024-06-13 DOI: 10.1039/d4qo00780h
Congcong Huang, Biyao Yang, Keying Zhang, Juan Li
Recent research has developed a Cu/Ru dual catalysis system for the hydroalkylation of racemic allylic alcohols and racemic ketimine esters. This method is distinguished by its ability to stereodivergently generate 1,4-nonadjacent stereocenters. This study employs density functional theory calculations to elucidate how copper and ruthenium synergistically drive this transformation and to reveal why this dual-catalyst system is more efficient than systems using either copper or ruthenium independently. The findings show how different combinations of chiral catalysts influence the formation of two stereogenic centers. We highlight the critical roles of noncovalent interactions and steric effects in determining the most energetically favorable transition states for each catalyst combination. Additionally, this study elucidates the significant role of potassium phosphate (K3PO4) in enhancing the reaction efficiency. Specifically, K3PO4 facilitates the dehydrogenation and hydrogenation processes across all three stages of the catalytic cycle. We also explore the reaction’s chemoselectivity by computing the formation mechanisms of three potential by-products and analyzing the driving forces behind the generation of the desired product. These mechanistic insights can support advancements in stereodivergent synthesis using cooperative bimetallic catalysis.
最近的研究开发了一种铜/钌双催化系统,用于外消旋烯丙基醇和外消旋酮亚胺酯的加氢烷基化反应。这种方法的特点是能够立体异构生成 1,4 非相邻立体中心。本研究利用密度泛函理论计算,阐明了铜和钌如何协同推动这种转化,并揭示了为什么这种双催化剂体系比单独使用铜或钌的体系更有效。研究结果表明,手性催化剂的不同组合如何影响两个立体中心的形成。我们强调了非共价相互作用和立体效应在决定每种催化剂组合最有利的能量转换状态中的关键作用。此外,本研究还阐明了磷酸二氢钾 (K3PO4) 在提高反应效率方面的重要作用。具体来说,K3PO4 在催化循环的所有三个阶段都促进了脱氢和加氢过程。我们还通过计算三种潜在副产物的形成机制和分析所需产物生成背后的驱动力,探索了该反应的化学选择性。这些机理方面的见解有助于利用合作双金属催化技术推进立体异构合成。
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引用次数: 0
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Organic Chemistry Frontiers
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