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Visible‐Light‐Initiated Uranyl‐Catalyzed Hydrosilylation and Hydrosulfonylation of Alkenes and Alkynes 可见光引发的铀催化烯烃和炔烃的氢硅烷化和氢磺酰化反应
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400745
Xingxing Gong , Qianyi Zhao , Congqing Zhu
This study investigates the visible‐light‐initiated uranyl(VI)‐catalyzed activation of Si−H bonds through direct hydrogen atom transfer, which facilitates the formation of silyl radicals from silanes. The silyl radical can abstract a chlorine atom from the sulfonyl chloride, leading to the generation of sulfonyl radicals. These silyl radicals and sulfonyl radicals could react with alkenes and alkynes, achieving the first example of uranyl‐catalyzed hydrosilylation and hydrosulfonylation of unsaturated C−C bonds. This method features mild reaction conditions and a broad substrate scope, and exhibits exceptional functional‐group tolerance. Consequently, it is suitable for the late‐stage functionalization of drug derivatives.
本研究探讨了可见光引发的铀酰(VI)催化活化 Si-H 键的过程,该过程通过直接氢原子转移促进硅烷中硅烷基的形成。硅烷基可从磺酰氯中抽取一个氯原子,从而生成磺酰基。这些硅基和磺酰基可与烯烃和炔烃发生反应,首次实现了铀酰催化的不饱和 C-C 键的氢硅化和氢磺化反应。这种方法的特点是反应条件温和,底物范围广泛,对官能团的耐受性极强。因此,它适用于药物衍生物的后期官能化。
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引用次数: 0
Ni‐Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings 镍催化炔烃的[2+2+2]环加成反应,在低催化剂添加量下生成烯和吡啶
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400765
M. Trinidad Martín , Celia Maya , Agustín Galindo , M. Carmen Nicasio
We report the Ni‐catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.
我们报告了镍催化的端炔环三聚反应,催化剂的负载量非常低(所有底物的负载量均为 0.05 摩尔%)。含有三联苯膦配体的镍催化剂只需 30 分钟就能在室温下完成反应,并在大多数情况下以单一异构体形式提供炔烃产物。实验数据和计算研究证明,单掺杂 PNi 物种参与了催化循环的所有基本步骤。
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引用次数: 0
Stereoselective Synthesis of Aliphatic α‐Amino Acids by Chemo‐Enzymatic Hydroamination‐Hydrodesulfurisation 化学-酶加氢胺-加氢脱硫法立体选择性合成脂肪族α-氨基酸
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401223
Celeste Nobbio , William R. Birmingham , Elisabetta Brenna , Nicholas J. Turner , Davide Tessaro , Fabio Parmeggiani
Phenylalanine ammonia lyase (PAL) enzymes have been extensively exploited to produce differently substituted arylalanine analogues, but their use in the stereoselective synthesis of aliphatic fatty amino acids has never been addressed. In this work, a two‐step hydroamination‐hydrodesulfurisation process has been investigated for the production of aliphatic L‐α‐amino acids from thienylacrylic acids, easily accessible by condensation from the corresponding arylaldehydes. Wild‐type PALs from Planctomyces brasiliensis and Streptomyces rimosus were selected as the most promising candidates and improved by site‐directed mutagenesis, thus unlocking the hydroamination of a broad panel of 10 different thienylacrylic acids bearing aliphatic and aromatic substituents. The subsequent hydrodesulfurisation step, accomplished by means of inexpensive Raney nickel in mild conditions and aqueous medium, afforded the corresponding aliphatic α‐amino acids in 10–63% overall isolated yield and perfect enantiopurity. This chemo‐enzymatic process represents the first example of aliphatic amino acid production using PALs, circumventing a major limitation of those biocatalysts.
苯丙氨酸解氨酶(PAL)酶已被广泛用于生产不同取代的芳基丙氨酸类似物,但它们在脂肪脂肪氨基酸的立体选择性合成中的应用从未得到解决。在这项工作中,研究了一种两步加氢胺-加氢脱硫工艺,用于从噻吩丙烯酸中生产脂肪族L-α-氨基酸,该工艺很容易通过相应的芳醛缩合得到。来自巴西plantomyces brasiliensis和链霉菌(Streptomyces rimosus)的野生型PALs被选为最有希望的候选基因,并通过位点定向诱变进行了改进,从而解锁了10种不同的含脂肪和芳香取代基的噻吩丙烯酸的氢胺化。随后的加氢脱硫步骤,在温和的条件和水介质中以廉价的兰尼镍完成,得到相应的脂肪族α-氨基酸,总分离率为10-63%,对映不纯性很好。这种化学酶促过程代表了第一个使用PALs生产脂肪族氨基酸的例子,绕过了这些生物催化剂的主要限制。
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引用次数: 0
N‐Heterocyclic Carbene‐Catalyzed Enantioselective Synthesis of Spirocyclohexane Oxindoles N-Heterocyclic Carbene-Catalyzed Enantioselective Synthesis of Spirocyclohexane Oxindoles(N-杂环碳烯催化的螺环己烷吲哚对映体选择性合成物
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401205
Ye Zhang , Zhoulu Wang , Min Ren , Xiaoxiang Zhang , Zhenqian Fu
A variety of structurally diverse spirocyclohexane oxindoles featuring a quaternary carbon centre have been successfully constructed through an N‐heterocyclic carbene‐catalyzed [4+2] annulation of isatin‐derived enals with α‐cyano‐β‐methylenones. This domino process exhibits a wide substrate tolerance, operates under mild conditions, and yields products with high enantioselectivities.
通过 N-杂环碳催化α-氰基-β-亚甲基烯酮与靛红衍生烯醛的[4+2]环化反应,成功地构建了具有季碳中心的多种结构不同的螺环己烷羰基吲哚。这种多米诺过程具有广泛的底物耐受性,操作条件温和,生成的产物具有很高的对映选择性。
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引用次数: 0
Three‐ and Seven‐membered Annulenones as a Lewis Base Catalyst for Enantioselective meso‐Epoxide Opening 三元和七元环烯酮作为路易斯碱催化剂对映选择性中环氧化合物打开
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401186
Sachie Arae , Yasushi Shimoda , Mizuki Kuwajima , Shunsuke Kotani , Makoto Nakajima
This is the report on the Lewis base catalysis of annulenones. Additionally, the synthesis of chiral annulenone catalysts and their application in asymmetric ring‐opening reactions of meso‐epoxides is shown. Annulenones, such as cyclopropenones and tropones, function as Lewis bases owing to their inherent polarity caused by aromaticity, resulting in the activation of silicon tetrachloride, which catalyzes the ring‐opening reaction of meso‐epoxides. Moreover, various chiral annulenone catalysts have been designed and synthesized, and microwave irradiation has been shown to improve the synthetic efficiency of chiral tropones. The chiral annulenones successfully catalyzed the asymmetric ring‐opening reaction of meso‐epoxides, resulting in the formation of 1,2‐chlorohydrins in a high yield and high enantioselectivity (up to 90% ee in 96% yield). These results represent the example of three‐ and seven‐membered annulenones as a chiral Lewis base catalyst.
这是关于环烯酮的路易斯碱催化作用的报告。此外,还介绍了手性环烯酮催化剂的合成及其在中介环氧化物不对称开环反应中的应用。环烯酮,如环丙烯酮和tropones,由于其固有的由芳香性引起的极性而发挥路易斯碱的作用,导致四氯化硅的活化,从而催化中介环氧化物的开环反应。此外,还设计和合成了多种手性环烯酮催化剂,并证明微波辐射可以提高手性环酮的合成效率。手性环烯酮成功地催化了中环氧化物的不对称开环反应,生成了高产率和高对映选择性的1,2 -氯丙烷(96%产率,高达90% ee)。这些结果代表了三元和七元环烯酮作为手性路易斯碱催化剂的例子。
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引用次数: 0
Molybdenum‐Catalyzed Direct Synthesis of Pyrroles from Nitroarenes with Glycols as Reductants 钼催化以乙二醇为还原剂从硝基烯烃直接合成吡咯类化合物
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401170
Sara Gómez‐Gil , Samuel Suárez‐Pantiga , María R. Pedrosa , Roberto Sanz
A molybdenum‐catalyzed synthesis of N‐(hetero)aryl pyrroles directly from inexpensive and commonly available (hetero)nitroarenes via reduction with pinacol and annulation with 1,4‐dicarbonyls or cyclobutane‐1,2‐diols has been described. The process does not require an inert atmosphere and tolerates the presence of air and water. This non‐noble catalytic system shows high chemoselectivity, allowing a diverse range of potentially reducible functional groups such as alkynes, alkenes, halogens, cyano, and carbonyls. Moreover, this strategy enables the reuse of a waste byproduct as reactant, facilitating the formation of challenging 1,4‐dicarbonyls from accessible cyclobutane‐1,2‐diols used as reducing agents.
本研究描述了一种钼催化的 N-(杂)芳基吡咯合成方法,该方法通过频哪醇还原和 1,4-二羰基或环丁烷-1,2-二醇环化,直接从廉价且常见的(杂)硝基烯烃合成 N-(杂)芳基吡咯。该工艺不需要惰性气氛,并能耐受空气和水的存在。这种非贵金属催化系统具有很高的化学选择性,可还原出多种潜在的官能团,如炔、烯、卤素、氰基和羰基。此外,这种策略还能将废弃的副产品作为反应物进行再利用,有助于从用作还原剂的可获得的环丁烷-1,2-二醇中形成具有挑战性的 1,4-二羰基。
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引用次数: 0
Silver and Copper‐Catalyzed Cycloaddition Reactions of Isocyanide Esters 银和铜催化的异氰酸酯环加成反应
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400994
Fatemeh Doraghi , Parsa Baghershahi , Farzad Gilaninezhad , Negar Mehdi Zadeh Darban , Navid Dastyafteh , Milad Noori , Mohammad Mahdavi
Owing to multiple reactive sites, such as an acidic α‐carbon and an isocyano group, isocyanide esters can successfully participate in the synthesis of various five‐ and six‐membered N‐heterocycles through the cycloaddition reactions under metal‐catalyzed systems. Considering the unique and versatile functionality of this synthon, in this review, we have highlighted silver and copper‐catalyzed cycloadditions of isocyanide esters over the last decade.
由于具有酸性 α 碳和异氰酸基等多个反应位点,异氰酸酯可在金属催化体系下通过环化反应成功参与合成各种五元和六元 N-heterocycles 。考虑到这种合成物的独特性和多功能性,我们在本综述中重点介绍了过去十年中银和铜催化的异氰酸酯环化反应。
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引用次数: 0
Amide synthesis via transaminative amidation of aromatic aldehydes/ketones: An entry to 15N isotopologs
IF 5.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401592
Jiaping Wu, Yufang Wang, Chaoying Fang, Yuhao Wang, Caiyang Kong, Xinghui Tao, Meihua Xie, Jitan Zhang
Herein, we develop the first one‐pot amide synthesis from aldehyde/ketone and amino acids via transaminative amidation reaction and the method requires no catalyst or promoters, by allowing a concise access to structurally diverse amides and lactams with good efficiency. This transformation could also proceed smoothly by direct use of ether solvent as the formylated reagent in stead of formylic acid, thus furnishing an unique synthesis of formamides. The underlying principles of this unique amide synthesis was rationalized by a series of mechanistic studies, which involved a concerted decarboxylatively structural isomerization/acylation process as the key for amidation and a transamination/imine formation/aerobic oxidation cascade for formamidation. The potential utility of this strategy has been demonstrated by the readily accessible late‐stage transformation of ​ biologically active molecules by 15N incorporating. This protocol was also applied to the total synthesis of a kind of drug Butenafine with 15N‐enrichment.
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引用次数: 0
Visible‐Light‐Induced Acyl and Thiocyano Pyridylation of Alkenes with Aldehyde and NH4SCN 可见光诱导烯醛和NH4SCN的酰基和硫代基吡啶化
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202401373
Xu Wang , Qi‐Xuan Jiang , Bi‐Yin Xiao , Wei Huang , Feng‐Hua Zhang
β‐pyridinyl ketones and β‐pyridinyl thiocyanates are commonly used as an essential organic synthesis intermediate and widely present in various drug molecules and bioactive molecules. Herein, a photoredox catalyzed acyl and thiocyano pyridylation of alkenes with aldehydes and NH4SCN via HAT and SET strategy respectively is described. This protocol employs more readily accessible aldehydes and NH4SCN as radical precursors under redox‐neutral conditions. Moreover, high atom economy, simple and accessible starting materials, late‐stage modification and wide substrate scope including primary, secondary alkyl aldehydes and aromatic aldehydes enable the potential application in the organic synthesis.
β-吡啶基酮和β-吡啶基硫氰酸酯是常用的有机合成中间体,广泛存在于各种药物分子和生物活性分子中。本文描述了光氧化还原催化烯烃与醛和NH4SCN的酰基和硫代基吡啶化,分别采用HAT和SET策略。该协议采用更容易接近的醛和NH4SCN作为自由基前体在氧化还原中性条件下。此外,高原子经济性、起始材料简单易得、后期修饰和广泛的底物范围(包括伯、仲烷基醛和芳香醛)使其在有机合成中具有潜在的应用前景。
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引用次数: 0
Arylation of Secondary Phosphines with Diaryliodonium Salts under Metal‐Free and Non‐Photochemical Conditions 在无金属和非光化学条件下用二重碘鎓盐芳基化仲膦
IF 4.4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2025-02-18 DOI: 10.1002/adsc.202400919
Ajit Kumar Jha , Sudeep Sarkar , Kacper Szczepanski , Marcin Kalek
A metal‐ and irradiation‐free approach for the direct arylation of secondary phosphines has been developed. The reaction employs diaryliodonium salts as electrophilic aryl‐transfer reagents, effecting the P−Ar bond‐formation in a single step, under mild conditions, using t‐BuOK as a base and DMSO as a solvent. The protocol furnishes expedient access to diverse unsymmetrical triarylphosphines and, upon a one‐pot oxidation, the corresponding triarylphosphine oxides. Experimental and computational studies support the inner sphere aryl‐transfer mechanism through a reductive coupling at the hypervalent iodine center. The calculations also point to a key role played by potassium ions, providing extra stabilization to the P−C bond‐forming transition state by binding the reactants via cation‐π interactions.
针对仲膦的直接芳基化,我们开发出了一种新型、高效、无金属、无辐照的方法。该反应采用二芳基碘鎓盐作为亲电芳基转移试剂,在温和的条件下,以叔丁氧钾为碱,二甲基亚砜为溶剂,在室温下一步完成 P-Ar 键的转化。该方法可以方便地获得各种非对称三芳基膦,并通过一锅氧化法获得相应的三芳基膦氧化物。实验和计算研究支持通过超价碘中心的还原耦合进行内球芳基转移的机制。计算结果还表明,钾离子发挥了关键作用,通过阳离子-π相互作用结合反应物,为形成 P-C 键的过渡态提供了额外的稳定性。
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引用次数: 0
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Advanced Synthesis & Catalysis
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